Fast method for identifying and assessing binder migration in lithium ion battery electrodes via glow discharge-sector field-mass spectrometry

Fast method for identifying and assessing binder migration in lithium ion battery electrodes via glow discharge-sector field-mass spectrometry | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Fast method for identifying and assessing binder migration in lithium ion battery electrodes via glow discharge-sector field-mass spectrometry Sascha Nowak, Stephen Dorn, Johanna Kauling, Markus Börner, Martin Winter, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9449468/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract A high amount of energy needed for the production of lithium ion batteries is used for the drying and solvent recovery of N -methyl-2-pyrrolidone (NMP) in electrodes with polyvinylidene fluoride-based binder (PVdF) systems. Therefore, controlling the amount of used solvent as well as developing efficient drying procedures is of major importance. Furthermore, the drying process and solid content of the electrode paste directly affect the battery performance due to the risk of transport of the binder towards the electrode surface. This work focuses on an analytical approach for rapidly and reliably assessing the degree of this migration by measuring the fluorine distribution via glow discharge-sector field-mass spectrometry (GD-SF-MS). A sample with notably more binder migration based on preliminary cross-section imaging via scanning electron microscopy combined with energy-dispersive X-ray spectroscopy and a reference sample with no visualized binder migration were evaluated, with the former displaying a severely elevated degree of binder migration over the reference based on GD-SF-MS analysis. The developed method could also be applicable to electrodes based on sodium carboxymethyl cellulose (Na-CMC) binders by investigating the Na distribution instead. Physical sciences/Materials science/Materials for energy and catalysis Physical sciences/Chemistry/Analytical chemistry/Mass spectrometry Binder: Migration LIBs SF-GD-MS Production Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Introduction One of the most important challenges the world faces for controlling the man-made climate change is the reduction carbon emissions by utilizing inherently fluctuating renewable energy sources instead of fossil fuels. 1 – 3 This entails the need for reliable energy storage technologies such as lithium ion batteries (LIBs). 3 – 5 First introduced commercially by Sony in 1991, 6–8 demand for them has increased radically ever since, 9,10 which is accompanied by an increasing energy demand for LIB manufacturing. 11 – 14 Roughly a third to half of all energy used in the production of LIBs can be attributed to the drying and solvent recovery in cathode manufacturing utilizing N -methyl-2-pyrrolodine (NMP) as the solvent in polyvinylidene fluoride (PVdF) binder systems. 12 , 14 – 16 It is therefore vital to optimize the solid content of the electrode paste as well as the drying procedure during processing to reduce the overall energy demand in LIB manufacturing. However, there are some limitations and challenges, as both the drying procedure and the amount of solvent used can directly affect the structural integrity and thus electrochemical performance of the electrodes due to a phenomenon called binder migration. 17 – 19 Binder migration, which is defined as the transport of binder material towards the electrode surface, is increasingly recognized as a critical factor governing electrode integrity and performance. 20 During the drying procedure in wet processing, capillary-driven convection and solvent evaporation can drive the PVdF binder and conductive agent (CA) (collectively referred to as carbon-binder domain, CBD) towards the outer regions of the electrode. 17 This non-uniform distribution detrimentally affects the particle-particle and particle-current collector contact, leading to an increased electronic resistance, reduced adhesive strength and accelerated capacity fade. 19 , 21 Therefore, the impact of different electrode paste formulations and drying procedures on the electrode need to be monitored and assessed continuously to ensure that any binder migration can be held to a minimum. 22 A recent study using pyrolysis gas chromatography hyphenated to mass spectrometry (Py-GC-MS) and cross-sectional secondary electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDX) visualized depth-dependent PVdF distributions in cathodes and correlated these gradients with drying temperatures. 17 Another study utilized the highly toxic and volatile osmium tetroxide (OsO 4 ) to stain the SBR binder fractions in negative electrodes and subsequently analyze the binder fractions via resin-embedded imaging. 23 Similarly, staining of SBR was also conducted recently utilizing silver nitride (AgNO 3 ) and bromine (Br 2 ). 24 A drawback to these methods is that they are time consuming, dangerous and require extensive sample preparation, which makes rapid and routine analysis parallel to electrode manufacturing unfeasible. Another analytical technique that can alleviate these shortcomings is glow discharge-sector field-mass spectrometry (GD-SF-MS). GD-SF-MS can analyze solid samples such as LIB electrodes directly by sputtering the sample via an argon (Ar) plasma and delivering an elemental depth-profile. 25 – 28 This technique offers several excellent qualities such as fast measurement times of as little as a few minutes, high and low sputter rates due to the possibility of a pulsed operation mode and a large range of measurable concentrations due to the triple detection mode of the sector field consisting of a Faraday cup and a secondary electron mulitplier. 29 , 30 Additionally, since solid samples can be analyzed directly, sample preparation is minimal for mechanically stable samples such as LIB electrodes. The different ionization mechanisms occurring in the GD ion source further allow for the ionization of fluorine (F), which is generally not possible for common plasma-based ionization methods such as inductively coupled plasmas (ICP) due to the higher excitation energy of F + compared to Ar + , 31 which would typically lead to a preferred ionization of Ar in the plasma over F. Since ionization occurs in the plasma’s afterglow, F may instead be ionized via high energy electron impact rather than thermal excitation or charge exchange as is the case in ICP-based ionization. 32 The lower Ar gas flow in GD systems (300 to 500 mL min − 1 ) compared to common ICP systems (10 to 20 L min − 1 ) further reduces the probability of a charge exchange between an ionized F + and an Ar atom in the plasma. This allows for the reliable analysis of F via GD-SF-MS, 33–35 as the medium and high resolutions of the SF-MS (≈ 4000 and ≈ 10,000 respectively) are sufficient to separate the 19 F peak from e.g. water-based ion interferences in the Ar supply ( 18 O 1 H + , 16 O 1 H 3 + , 17 O 2 H + , 16 O 1 H 2 2 H + etc.). In the context of this work, GD-SF-MS can serve as a powerful analytical method for assessing the PVdF distribution in electrode samples based on the F signal. This study examines two different NCM622 (LiNi 0.6 Co 0.2 Mn 0.2 O 2 , lithium nickel (Ni) cobalt (Co) manganese (Mn) oxide) cathode formulations, reference samples (ref. samples) and samples with notable binder migration (samples A - C) based on preliminary SEM-EDX investigations. The samples were then analyzed via GD-SF-MS to acquire depth-resolved F signals to evaluate whether differences in the degree of binder migration can be identified reliably. Results and discussion SEM and EDX imaging for the cross-section of a cathode sample displaying pronounced binder migration can be seen in Fig. 1 . The SEM image (Fig. 1 a) depicts the polished surface of the cross-section with densely packed NCM622 particles with typical polycrystalline morphology. Interstitial regions between the active material particles are filled with a darker-shaded matrix, which can be attributed to the amorphous CBD. The sample further displays a non-uniform porosity distribution, with larger voids visible in the upper regions of the electrode. The corresponding C Kα1 map (Fig. 1 b) depicts a heterogeneous distribution of C throughout the electrode’s thickness. A pronounced increase can be seen towards the upper regions of the electrode, indicating an enrichment of carbon-containing species such as the binder itself and the CA. Within the bulk of the electrode, the C signal is localized along the interparticle boundaries. Given that both the PVdF binder as well as the CA contain carbon, it can be concluded that the accumulation of it towards the surface of the electrode can be attributed to binder migration during processing. After the identification of the CBD distribution via cross-section imaging, GD-SF-MS analysis was conducted for a reference sample as well as the identified binder migration sample A. Exemplary results for the elemental distribution of Li, C, Mn, Ni and Co in sample A can be seen in Fig. 2 a. The ion beam ratio (IBR) is depicted on the y-axis and represents the relative signal intensity of an element compared to the sum of measured intensities of all elements and serves as a parameter that excludes plasma or excitation instabilities within a measurement. 27 , 36 , 37 The IBRs are calculated according to Supplementary Eq. 1 in the SI. The measurement reveals a notable increase of the C IBR at the surface of the electrode with up to 6.0·10 5 ppm. This drops down to a stable 0.8·10 5 ppm after around 15 minutes of sputtering, indicating that the bulk of the electrode is fully reached by this time. Correspondingly, the IBRs of Li and the transition metals begin at lower values at the start of the measurement. These IBRs increase sharply over the first 2 to 3 minutes of sputtering, reaching stable values after 9 to 12 minutes. This behavior can be explained by accumulation of carbon containing species at the surface of the electrode, which aligns well with results obtained via SEM-EDX imaging. Carbon contamination at the sample surface is a common occurrence in sensitive surface analysis, 38–41 as any organic contamination and the adsorption of gases such as carbon dioxide or other organic volatile compounds at the sample surface directly impact the carbon signal obtained with these measurements. Additionally, other carbon containing compounds such as carbonates originating from the sample itself (e.g. residual carbonate species from the active material precursors) can further influence the carbon signal obtained. The increased C IBR therefore does not exclusively represent the migration of the carbon containing binder and CA, which is why the F distribution was investigated more closely and in direct comparison with the results for the reference sample in Fig. 2 b. Here the IBRs show a similar profile to the C IBRs obtained for sample A. While the measurement starts out with relatively lower F contents during the first few seconds for both sample A as well as the reference sample (421 ppm and 331 ppm respectively), a sharp increase to a local maximum can be identified for both samples as well, reaching values of up to 701 ppm for the sample A and 424 ppm for the reference sample, which then fade into a stable bulk content after around 15 minutes. These results indicate that reference sample also depicts a detectable level of binder migration, since even a controlled evaporation of solvent would naturally lead to a certain amount of binder being dragged towards the surface of the electrode through capillary-driven convection during the drying process. 17 Regardless, in addition to the overall higher F IBRs obtained for sample A, the results still present a qualitative difference in the F distribution between the two samples. Sample A depicts a notably broader F distribution at the surface compared to the reference sample, which may be attributed to a more pronounced accumulation of the PVdF binder at the surface. A plasma ignition check was performed further to ensure that the gradients at the surface were not influenced by the plasma ignition causing a change in the initial excitation behavior during analysis. This means that after sample A was measured initially, it was removed from the instrument and kept at normal atmosphere for one day. Afterwards, a second measurement of the same sample on the already sputtered area was conducted. The results of that measurement can be seen in Fig. 3 . Overall, the IBRs for all elements show stable signals throughout the entire measurement due to already having reached the bulk material in the initial measurement void of any binder accumulation (Fig. 3 a). The exception is a short deviation during the first few seconds of analysis. During this, an elevation of the Li and C IBRs can be observed which causes a decrease in the IBRs of the transition metals and leaves the F IBR unaffected (Fig. 3 b). This can likely be attributed to the formation of lithium carbonate on the surface of the already sputtered material due to the increased reactivity of the freshly exposed material surface against the moisture in the atmosphere. Since this effect appears to be notably smaller than the concentration gradients that could be observed during the initial measurement, it can be concluded that the ignition of the plasma itself has no impact on the excitation behavior at the start of the measurement. Thus, it can be excluded as a contributing factor to the F gradient that can be observed in the samples. For a more adequate direct comparison between the degrees of binder migration in the different samples, the F IBRs for sample A and a reference sample were normalized to their own maximum value and integrated at the time of analysis at which the F IBR reaches 15% of its maximum. For the reference sample this means the majority of migrated binder was sputtered in the first 4.2 minutes of the measurement, and for sample A it took 9.6 minutes to reach the same relative F signal. These results can be seen in Fig. 4 . While the normalization naturally eliminates the higher F IBRs in sample A, the overall broader peak of the F signal persists (Fig. 4 a). This can be attributed to an increased accumulation of the binder at the surface of the electrode compared to the reference sample due to more binder migrating towards the upper regions during the drying process. This is also reflected in the integrated areas. The area for sample A with more pronounced binder migration amounts to 388 min·% and the area for the reference sample to 129 min·%. This represents an increase of 201% over the reference sample, which means that the layer of the cathode that consists of an elevated amount of binder compared to the bulk material is severely larger in sample A compared to the reference sample. Conclusion Based on preliminary SEM-EDX, this study could show that sample A with CBD accumulation in the upper electrode layers displayed a notably higher level of binder migration compared to the reference sample based on the investigated F distribution. However, according to results obtained via GD-SF-MS, even the reference sample displayed a low level of binder migration that may be challenging to detect with more conventional analysis methods such as SEM-EDX cross-section imaging. This can be attributed to the GD system’s unique ability to ionize and detect F, which makes it more reliable and sensitive at identifying binder fractions in the electrode regions compared to using the carbon signal. A schematic summary of the method and results obtained in this study can be seen in Fig. 5 . Overall, GD-SF-MS can serve as a potent tool in conducting rapid analysis of electrodes to identify binder migration. In addition to investigating F-based binder systems, which was shown in this work, other systems utilizing e.g. Na-CMC should also be assessable. The analysis requires minimal sample preparation and achieves reliable and reproducible results (see Supplementary Fig. 1 in the SI) in as little as 15 minutes, which is crucial for assessing and monitoring binder migration parallel to optimization of the drying process as part of manufacturing. Experimental Electrode and sample preparation Electrodes were formulated using a ratio of 95/2/3 wt.% of NCM622 (BASF, Ludwigshafen, Germany)/Super C65 as CA (Imerys Graphite & Carbon, Paris, France)/PVdF (Sigma Aldrich, Burlington, MA, USA). The solid content of the reference electrode paste was set to 80%, the solid content of the electrodes displaying elevated binder migration was set to 73%. After dissolving the binder in NMP (Sigma Aldrich, Burlington, MA, USA), prepared dry mixtures of the NCM622 and CA were added and dispersed for 40 minutes at 4000 rpm (Dispermat CV3-Plus, VMA-Getzmann, Reichshof, Germany). The resulting paste was coated on aluminum foil using a doctor blade, and oven-drying was conducted for 2 hours at 80°C. The electrode sheets were then calendered to a porosity of 30%. Electrodes for GD-SF-MS analysis were punched into circular samples with a diameter of 12 mm using a handheld puncher. Cross-section preparation of samples was conducted using an IB-19540CCP cooling cross section polisher (Jeol, Akishima, Tokyo, Japan) with an acceleration voltage of 5 kV and an additional smoothing step at 2 kV. Scanning electron microscopy and energy-dispersive X-ray spectroscopy SEM imaging was conducted using an Auriga CrossBeam 550 workstation (Zeiss, Oberkochen, Germany) equipped with a Schottky-type field emission gun and an acceleration voltage of 3 kV. EDX imaging was conducted using an Ultim Extreme detector (Oxford Instruments, High Wycombe, England) with an acceleration voltage of 15 kV. Evaluation was conducted using the AZtech software (Oxford Instruments, High Wycombe, England). Glow discharge-sector field-mass spectrometry GD-SF-MS analysis in pulsed-mode was conducted using a Thermo Element GD Plus (Thermo Scientific, Bremen, Germany). Measurements of samples with notable binder migration and reference samples were conducted three times, representative data of one measurement for each sample is shown in this study. The prepared electrode samples were attached to a brass sample holder using a double-sided adhesive pad (Plano, Wetzlar, Germany) and inserted into the instrument. For the plasma ignition check, the sample was removed after initial measurement, stored at normal atmosphere for one day and subsequently analyzed a second time. Analysis parameters were applied according to Table 1 . Masses for all detected elements ( 7 Li, 12 C, 19 F, 55 Mn, 58 Ni, 59 Co) were acquired at medium resolution (≈ 4000). Table 1 Overview of instrument parameters used for GD-SF-MS analysis. Plasma voltage 1000 V Plasma current 8 mA Ar gas flow 450 mL min − 1 Pulse duration 10 µs Pulse frequency 4 kHz Cooling temperature 0 °C Anode cap size 8 mm Declarations Conflict of Interest The authors declare no conflict of interest. Author contributions Conceptualization: S.L. Dorn; Methodology: S.L. Dorn (GD-SF-MS), J. Kauling (SEM-EDX, electrode preparation); Writing: S.L. Dorn; Review and editing: J. Kauling, M. Börner, M. Winter, S. Wiemers-Meyer, S. Nowak. Acknowledgements The authors thank the German Federal Ministry of Education and Research (BMBF) for funding the project “BatGasMod” (03XP0311C). This work was additionally supported by the project 21GRD01 (OpMetBat), which received funding from the European Partnership on Metrology, cofinanced by the European Union’s Horizon Europe Research and Innovation Programme and by the Participating States. The authors would further like to thank Andre Bar for graphics support. Data availability The generated datasets that support the findings of this study are available from the corresponding author upon reasonable request. References Erdiwansyah et al. A critical review of the integration of renewable energy sources with various technologies. Protection and Control of Modern Power Systems 6; 10.1186/s41601-021-00181-3 (2021). Zhao, J. et al. The determinants of renewable energy sources for the fueling of green and sustainable economy. Energy 238, 122029; 10.1016/j.energy.2021.122029 (2022). Halkos, G. E. & Gkampoura, E.-C. Reviewing Usage, Potentials, and Limitations of Renewable Energy Sources. 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Analytica Chimica Acta 679, 7–16; 10.1016/j.aca.2010.08.031 (2010). Köhler, R., Hellrung, D., Tasche, D. & Gerhard, C. Quantification of Carbonic Contamination of Fused Silica Surfaces at Different Stages of Classical Optics Manufacturing. Materials 14; 10.3390/ma14071620 (2021). Fairley, N., Bargiela, P. & Baltrusaitis, J. Surface analysis insight note: Illustrating the effect of adventitious contamination on Pt photoemission peak intensities. Surface and Interface Analysis 56, 122–125; 10.1002/sia.7276 (2024). Additional Declarations There is NO Competing Interest. Supplementary Files DornetalSI.docx Supporting Information Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-9449468","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":627658186,"identity":"198fef45-a677-4de3-9c4c-552f76b4f593","order_by":0,"name":"Sascha Nowak","email":"data:image/png;base64,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","orcid":"https://orcid.org/0000-0003-1508-6073","institution":"University of Münster","correspondingAuthor":true,"prefix":"","firstName":"Sascha","middleName":"","lastName":"Nowak","suffix":""},{"id":627658187,"identity":"d181a97f-2efc-4875-936b-bcbee24d4d29","order_by":1,"name":"Stephen Dorn","email":"","orcid":"https://orcid.org/0000-0002-6121-7591","institution":"University of Münster","correspondingAuthor":false,"prefix":"","firstName":"Stephen","middleName":"","lastName":"Dorn","suffix":""},{"id":627658188,"identity":"6f273a2e-8a01-4156-ab78-c4efba9123fa","order_by":2,"name":"Johanna Kauling","email":"","orcid":"","institution":"University of Münster","correspondingAuthor":false,"prefix":"","firstName":"Johanna","middleName":"","lastName":"Kauling","suffix":""},{"id":627658189,"identity":"663ac71e-0385-4a4a-952a-8e2fc2543623","order_by":3,"name":"Markus Börner","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Markus","middleName":"","lastName":"Börner","suffix":""},{"id":627658190,"identity":"dba01321-0c47-4325-abfb-17e625c8ca3a","order_by":4,"name":"Martin Winter","email":"","orcid":"https://orcid.org/0000-0003-4176-5811","institution":"MEET Battery Research Center at the University of Münster \u0026 Helmholtz Institute Münster (IMD-4) of Forschungszentrum Jülich","correspondingAuthor":false,"prefix":"","firstName":"Martin","middleName":"","lastName":"Winter","suffix":""},{"id":627658191,"identity":"fb814d70-0a0a-40bf-84f4-f8840b9a9fea","order_by":5,"name":"Simon Wiemers-Meyer","email":"","orcid":"https://orcid.org/0000-0001-8608-4521","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Simon","middleName":"","lastName":"Wiemers-Meyer","suffix":""}],"badges":[],"createdAt":"2026-04-17 13:05:45","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-9449468/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-9449468/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":108493047,"identity":"1395dd48-741d-42bd-a35b-ce0028645abb","added_by":"auto","created_at":"2026-05-05 09:59:17","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":890234,"visible":true,"origin":"","legend":"\u003cp\u003eImaging of a cross section of an NCM622 sample displaying an accumulation of the CBD at the surface of the electrode. Panel (a) depicts an electron image using SEM, while panel (b) depicts the carbon signal using EDX imaging.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-9449468/v1/550b66340e81809a7dbc7ddd.png"},{"id":108406150,"identity":"613b554b-88d6-4ab7-abce-b6aec1aad347","added_by":"auto","created_at":"2026-05-04 09:41:31","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":159899,"visible":true,"origin":"","legend":"\u003cp\u003eResults for GD-SF-MS analysis of two NMC622 cathode samples. Panel (a) depicts the elemental depth profile of major elements (Li, C, Mn, Co, Ni) from sample A with notable binder migration via their calculated ion beam ratios (IBRs). Panel (b) depicts the respective F IBRs for both the sample A as well as the reference sample.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-9449468/v1/5c79cf600e56c6c1e8ad760c.png"},{"id":108406146,"identity":"89e22976-04e1-4a27-89ef-f453cfb0d86b","added_by":"auto","created_at":"2026-05-04 09:41:30","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":126678,"visible":true,"origin":"","legend":"\u003cp\u003eResults for the second GD-SF-MS analysis of the NCM622 sample A after initial sputtering, subsequent removal and storage at normal atmosphere for a day. Panel (a) depicts the elemental depth profile of all measured elements via their calculated IBRs, panel (b) depicts the zoomed in IBRs for F for visibility purposes.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-9449468/v1/1a9df51c5f7e0b7d01fa3675.png"},{"id":108493633,"identity":"c81d8e89-1d9a-4202-8500-d315de424bdd","added_by":"auto","created_at":"2026-05-05 10:01:07","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":197343,"visible":true,"origin":"","legend":"\u003cp\u003ePanel (a) depicts normalized F IBRs for the reference NCM622 sample and sample A, as well as integrated areas from x = 0 min to the x value at which the respective normalized F IBR reaches 15 % of its maximum value. Panel (b) depicts the corresponding integrated area values.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-9449468/v1/6a087b5fc27da4125a3b5fd1.png"},{"id":108493152,"identity":"6e2936ef-3c49-4d5a-a4df-85020dde3a3b","added_by":"auto","created_at":"2026-05-05 09:59:30","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":716865,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic depiction of the binder migration assessment conducted via GD-SF-MS. Higher F-containing binder fractions in the upper electrode regions of the electrode result in a decreasing F signal throughout GD-SF-MS analysis.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-9449468/v1/e445f846409ad19f762dfe11.png"},{"id":108804024,"identity":"4ed58eab-ff64-40aa-a174-9faab1f89197","added_by":"auto","created_at":"2026-05-08 15:14:39","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2219543,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9449468/v1/f9290202-2189-46cc-8d66-fa342741d4ec.pdf"},{"id":108406145,"identity":"80329f85-8a80-415a-aa7e-25740d645d06","added_by":"auto","created_at":"2026-05-04 09:41:30","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":223197,"visible":true,"origin":"","legend":"Supporting Information","description":"","filename":"DornetalSI.docx","url":"https://assets-eu.researchsquare.com/files/rs-9449468/v1/0a5d387494c0489ab23351c5.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Fast method for identifying and assessing binder migration in lithium ion battery electrodes via glow discharge-sector field-mass spectrometry","fulltext":[{"header":"Introduction","content":"\u003cp\u003eOne of the most important challenges the world faces for controlling the man-made climate change is the reduction carbon emissions by utilizing inherently fluctuating renewable energy sources instead of fossil fuels.\u003csup\u003e\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e This entails the need for reliable energy storage technologies such as lithium ion batteries (LIBs).\u003csup\u003e\u003cspan additionalcitationids=\"CR4\" citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e First introduced commercially by Sony in 1991,\u003csup\u003e6\u0026ndash;8\u003c/sup\u003e demand for them has increased radically ever since,\u003csup\u003e9,10\u003c/sup\u003e which is accompanied by an increasing energy demand for LIB manufacturing.\u003csup\u003e\u003cspan additionalcitationids=\"CR12 CR13\" citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e Roughly a third to half of all energy used in the production of LIBs can be attributed to the drying and solvent recovery in cathode manufacturing utilizing \u003cem\u003eN\u003c/em\u003e-methyl-2-pyrrolodine (NMP) as the solvent in polyvinylidene fluoride (PVdF) binder systems.\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e,\u003cspan additionalcitationids=\"CR15\" citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e It is therefore vital to optimize the solid content of the electrode paste as well as the drying procedure during processing to reduce the overall energy demand in LIB manufacturing. However, there are some limitations and challenges, as both the drying procedure and the amount of solvent used can directly affect the structural integrity and thus electrochemical performance of the electrodes due to a phenomenon called binder migration.\u003csup\u003e\u003cspan additionalcitationids=\"CR18\" citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e Binder migration, which is defined as the transport of binder material towards the electrode surface, is increasingly recognized as a critical factor governing electrode integrity and performance.\u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e During the drying procedure in wet processing, capillary-driven convection and solvent evaporation can drive the PVdF binder and conductive agent (CA) (collectively referred to as carbon-binder domain, CBD) towards the outer regions of the electrode.\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e This non-uniform distribution detrimentally affects the particle-particle and particle-current collector contact, leading to an increased electronic resistance, reduced adhesive strength and accelerated capacity fade.\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e,\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e Therefore, the impact of different electrode paste formulations and drying procedures on the electrode need to be monitored and assessed continuously to ensure that any binder migration can be held to a minimum.\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eA recent study using pyrolysis gas chromatography hyphenated to mass spectrometry (Py-GC-MS) and cross-sectional secondary electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDX) visualized depth-dependent PVdF distributions in cathodes and correlated these gradients with drying temperatures.\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e Another study utilized the highly toxic and volatile osmium tetroxide (OsO\u003csub\u003e4\u003c/sub\u003e) to stain the SBR binder fractions in negative electrodes and subsequently analyze the binder fractions \u003cem\u003evia\u003c/em\u003e resin-embedded imaging.\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e Similarly, staining of SBR was also conducted recently utilizing silver nitride (AgNO\u003csub\u003e3\u003c/sub\u003e) and bromine (Br\u003csub\u003e2\u003c/sub\u003e).\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eA drawback to these methods is that they are time consuming, dangerous and require extensive sample preparation, which makes rapid and routine analysis parallel to electrode manufacturing unfeasible. Another analytical technique that can alleviate these shortcomings is glow discharge-sector field-mass spectrometry (GD-SF-MS). GD-SF-MS can analyze solid samples such as LIB electrodes directly by sputtering the sample \u003cem\u003evia\u003c/em\u003e an argon (Ar) plasma and delivering an elemental depth-profile.\u003csup\u003e\u003cspan additionalcitationids=\"CR26 CR27\" citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e This technique offers several excellent qualities such as fast measurement times of as little as a few minutes, high and low sputter rates due to the possibility of a pulsed operation mode and a large range of measurable concentrations due to the triple detection mode of the sector field consisting of a Faraday cup and a secondary electron mulitplier.\u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e,\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e Additionally, since solid samples can be analyzed directly, sample preparation is minimal for mechanically stable samples such as LIB electrodes. The different ionization mechanisms occurring in the GD ion source further allow for the ionization of fluorine (F), which is generally not possible for common plasma-based ionization methods such as inductively coupled plasmas (ICP) due to the higher excitation energy of F\u003csup\u003e+\u003c/sup\u003e compared to Ar\u003csup\u003e+\u003c/sup\u003e,\u003csup\u003e31\u003c/sup\u003e which would typically lead to a preferred ionization of Ar in the plasma over F. Since ionization occurs in the plasma\u0026rsquo;s afterglow, F may instead be ionized \u003cem\u003evia\u003c/em\u003e high energy electron impact rather than thermal excitation or charge exchange as is the case in ICP-based ionization.\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e The lower Ar gas flow in GD systems (300 to 500 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) compared to common ICP systems (10 to 20 L min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) further reduces the probability of a charge exchange between an ionized F\u003csup\u003e+\u003c/sup\u003e and an Ar atom in the plasma. This allows for the reliable analysis of F \u003cem\u003evia\u003c/em\u003e GD-SF-MS,\u003csup\u003e33\u0026ndash;35\u003c/sup\u003e as the medium and high resolutions of the SF-MS (\u0026asymp;\u0026thinsp;4000 and \u0026asymp;\u0026thinsp;10,000 respectively) are sufficient to separate the \u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003eF peak from e.g. water-based ion interferences in the Ar supply (\u003csup\u003e18\u003c/sup\u003eO\u003csup\u003e1\u003c/sup\u003eH\u003csup\u003e+\u003c/sup\u003e, \u003csup\u003e16\u003c/sup\u003eO\u003csup\u003e1\u003c/sup\u003eH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e, \u003csup\u003e17\u003c/sup\u003eO\u003csup\u003e2\u003c/sup\u003eH\u003csup\u003e+\u003c/sup\u003e, \u003csup\u003e16\u003c/sup\u003eO\u003csup\u003e1\u003c/sup\u003eH\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e2\u003c/sup\u003eH\u003csup\u003e+\u003c/sup\u003e etc.).\u003c/p\u003e \u003cp\u003eIn the context of this work, GD-SF-MS can serve as a powerful analytical method for assessing the PVdF distribution in electrode samples based on the F signal. This study examines two different NCM622 (LiNi\u003csub\u003e0.6\u003c/sub\u003eCo\u003csub\u003e0.2\u003c/sub\u003eMn\u003csub\u003e0.2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, lithium nickel (Ni) cobalt (Co) manganese (Mn) oxide) cathode formulations, reference samples (ref. samples) and samples with notable binder migration (samples A - C) based on preliminary SEM-EDX investigations. The samples were then analyzed \u003cem\u003evia\u003c/em\u003e GD-SF-MS to acquire depth-resolved F signals to evaluate whether differences in the degree of binder migration can be identified reliably.\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cp\u003eSEM and EDX imaging for the cross-section of a cathode sample displaying pronounced binder migration can be seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe SEM image (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea) depicts the polished surface of the cross-section with densely packed NCM622 particles with typical polycrystalline morphology. Interstitial regions between the active material particles are filled with a darker-shaded matrix, which can be attributed to the amorphous CBD. The sample further displays a non-uniform porosity distribution, with larger voids visible in the upper regions of the electrode. The corresponding C Kα1 map (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb) depicts a heterogeneous distribution of C throughout the electrode\u0026rsquo;s thickness. A pronounced increase can be seen towards the upper regions of the electrode, indicating an enrichment of carbon-containing species such as the binder itself and the CA. Within the bulk of the electrode, the C signal is localized along the interparticle boundaries. Given that both the PVdF binder as well as the CA contain carbon, it can be concluded that the accumulation of it towards the surface of the electrode can be attributed to binder migration during processing.\u003c/p\u003e \u003cp\u003eAfter the identification of the CBD distribution \u003cem\u003evia\u003c/em\u003e cross-section imaging, GD-SF-MS analysis was conducted for a reference sample as well as the identified binder migration sample A. Exemplary results for the elemental distribution of Li, C, Mn, Ni and Co in sample A can be seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea. The ion beam ratio (IBR) is depicted on the y-axis and represents the relative signal intensity of an element compared to the sum of measured intensities of all elements and serves as a parameter that excludes plasma or excitation instabilities within a measurement.\u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e,\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e,\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e The IBRs are calculated according to Supplementary Eq.\u0026nbsp;1 in the SI.\u003c/p\u003e \u003cp\u003eThe measurement reveals a notable increase of the C IBR at the surface of the electrode with up to 6.0\u0026middot;10\u003csup\u003e5\u003c/sup\u003e ppm. This drops down to a stable 0.8\u0026middot;10\u003csup\u003e5\u003c/sup\u003e ppm after around 15 minutes of sputtering, indicating that the bulk of the electrode is fully reached by this time. Correspondingly, the IBRs of Li and the transition metals begin at lower values at the start of the measurement. These IBRs increase sharply over the first 2 to 3 minutes of sputtering, reaching stable values after 9 to 12 minutes.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThis behavior can be explained by accumulation of carbon containing species at the surface of the electrode, which aligns well with results obtained \u003cem\u003evia\u003c/em\u003e SEM-EDX imaging. Carbon contamination at the sample surface is a common occurrence in sensitive surface analysis,\u003csup\u003e38\u0026ndash;41\u003c/sup\u003e as any organic contamination and the adsorption of gases such as carbon dioxide or other organic volatile compounds at the sample surface directly impact the carbon signal obtained with these measurements. Additionally, other carbon containing compounds such as carbonates originating from the sample itself (e.g. residual carbonate species from the active material precursors) can further influence the carbon signal obtained. The increased C IBR therefore does not exclusively represent the migration of the carbon containing binder and CA, which is why the F distribution was investigated more closely and in direct comparison with the results for the reference sample in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb.\u003c/p\u003e \u003cp\u003eHere the IBRs show a similar profile to the C IBRs obtained for sample A. While the measurement starts out with relatively lower F contents during the first few seconds for both sample A as well as the reference sample (421 ppm and 331 ppm respectively), a sharp increase to a local maximum can be identified for both samples as well, reaching values of up to 701 ppm for the sample A and 424 ppm for the reference sample, which then fade into a stable bulk content after around 15 minutes. These results indicate that reference sample also depicts a detectable level of binder migration, since even a controlled evaporation of solvent would naturally lead to a certain amount of binder being dragged towards the surface of the electrode through capillary-driven convection during the drying process.\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e Regardless, in addition to the overall higher F IBRs obtained for sample A, the results still present a qualitative difference in the F distribution between the two samples. Sample A depicts a notably broader F distribution at the surface compared to the reference sample, which may be attributed to a more pronounced accumulation of the PVdF binder at the surface.\u003c/p\u003e \u003cp\u003eA plasma ignition check was performed further to ensure that the gradients at the surface were not influenced by the plasma ignition causing a change in the initial excitation behavior during analysis. This means that after sample A was measured initially, it was removed from the instrument and kept at normal atmosphere for one day. Afterwards, a second measurement of the same sample on the already sputtered area was conducted. The results of that measurement can be seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e.\u003c/p\u003e \u003cp\u003eOverall, the IBRs for all elements show stable signals throughout the entire measurement due to already having reached the bulk material in the initial measurement void of any binder accumulation (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea). The exception is a short deviation during the first few seconds of analysis. During this, an elevation of the Li and C IBRs can be observed which causes a decrease in the IBRs of the transition metals and leaves the F IBR unaffected (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb). This can likely be attributed to the formation of lithium carbonate on the surface of the already sputtered material due to the increased reactivity of the freshly exposed material surface against the moisture in the atmosphere. Since this effect appears to be notably smaller than the concentration gradients that could be observed during the initial measurement, it can be concluded that the ignition of the plasma itself has no impact on the excitation behavior at the start of the measurement. Thus, it can be excluded as a contributing factor to the F gradient that can be observed in the samples.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFor a more adequate direct comparison between the degrees of binder migration in the different samples, the F IBRs for sample A and a reference sample were normalized to their own maximum value and integrated at the time of analysis at which the F IBR reaches 15% of its maximum. For the reference sample this means the majority of migrated binder was sputtered in the first 4.2 minutes of the measurement, and for sample A it took 9.6 minutes to reach the same relative F signal. These results can be seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eWhile the normalization naturally eliminates the higher F IBRs in sample A, the overall broader peak of the F signal persists (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea). This can be attributed to an increased accumulation of the binder at the surface of the electrode compared to the reference sample due to more binder migrating towards the upper regions during the drying process. This is also reflected in the integrated areas. The area for sample A with more pronounced binder migration amounts to 388 min\u0026middot;% and the area for the reference sample to 129 min\u0026middot;%. This represents an increase of 201% over the reference sample, which means that the layer of the cathode that consists of an elevated amount of binder compared to the bulk material is severely larger in sample A compared to the reference sample.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eBased on preliminary SEM-EDX, this study could show that sample A with CBD accumulation in the upper electrode layers displayed a notably higher level of binder migration compared to the reference sample based on the investigated F distribution. However, according to results obtained \u003cem\u003evia\u003c/em\u003e GD-SF-MS, even the reference sample displayed a low level of binder migration that may be challenging to detect with more conventional analysis methods such as SEM-EDX cross-section imaging. This can be attributed to the GD system\u0026rsquo;s unique ability to ionize and detect F, which makes it more reliable and sensitive at identifying binder fractions in the electrode regions compared to using the carbon signal. A schematic summary of the method and results obtained in this study can be seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eOverall, GD-SF-MS can serve as a potent tool in conducting rapid analysis of electrodes to identify binder migration. In addition to investigating F-based binder systems, which was shown in this work, other systems utilizing e.g. Na-CMC should also be assessable. The analysis requires minimal sample preparation and achieves reliable and reproducible results (see Supplementary Fig.\u0026nbsp;1 in the SI) in as little as 15 minutes, which is crucial for assessing and monitoring binder migration parallel to optimization of the drying process as part of manufacturing.\u003c/p\u003e"},{"header":"Experimental","content":"\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003eElectrode and sample preparation\u003c/h2\u003e \u003cp\u003eElectrodes were formulated using a ratio of 95/2/3 wt.% of NCM622 (BASF, Ludwigshafen, Germany)/Super C65 as CA (Imerys Graphite \u0026amp; Carbon, Paris, France)/PVdF (Sigma Aldrich, Burlington, MA, USA). The solid content of the reference electrode paste was set to 80%, the solid content of the electrodes displaying elevated binder migration was set to 73%. After dissolving the binder in NMP (Sigma Aldrich, Burlington, MA, USA), prepared dry mixtures of the NCM622 and CA were added and dispersed for 40 minutes at 4000 rpm (Dispermat CV3-Plus, VMA-Getzmann, Reichshof, Germany). The resulting paste was coated on aluminum foil using a doctor blade, and oven-drying was conducted for 2 hours at 80\u0026deg;C. The electrode sheets were then calendered to a porosity of 30%.\u003c/p\u003e \u003cp\u003eElectrodes for GD-SF-MS analysis were punched into circular samples with a diameter of 12 mm using a handheld puncher. Cross-section preparation of samples was conducted using an IB-19540CCP cooling cross section polisher (Jeol, Akishima, Tokyo, Japan) with an acceleration voltage of 5 kV and an additional smoothing step at 2 kV.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eScanning electron microscopy and energy-dispersive X-ray spectroscopy\u003c/h3\u003e\n\u003cp\u003eSEM imaging was conducted using an Auriga CrossBeam 550 workstation (Zeiss, Oberkochen, Germany) equipped with a Schottky-type field emission gun and an acceleration voltage of 3 kV. EDX imaging was conducted using an Ultim Extreme detector (Oxford Instruments, High Wycombe, England) with an acceleration voltage of 15 kV. Evaluation was conducted using the AZtech software (Oxford Instruments, High Wycombe, England).\u003c/p\u003e\n\u003ch3\u003eGlow discharge-sector field-mass spectrometry\u003c/h3\u003e\n\u003cp\u003eGD-SF-MS analysis in pulsed-mode was conducted using a Thermo Element GD Plus (Thermo Scientific, Bremen, Germany). Measurements of samples with notable binder migration and reference samples were conducted three times, representative data of one measurement for each sample is shown in this study. The prepared electrode samples were attached to a brass sample holder using a double-sided adhesive pad (Plano, Wetzlar, Germany) and inserted into the instrument. For the plasma ignition check, the sample was removed after initial measurement, stored at normal atmosphere for one day and subsequently analyzed a second time. Analysis parameters were applied according to Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. Masses for all detected elements (\u003csup\u003e7\u003c/sup\u003eLi, \u003csup\u003e12\u003c/sup\u003eC, \u003csup\u003e19\u003c/sup\u003eF, \u003csup\u003e55\u003c/sup\u003eMn, \u003csup\u003e58\u003c/sup\u003eNi, \u003csup\u003e59\u003c/sup\u003eCo) were acquired at medium resolution (\u0026asymp;\u0026thinsp;4000).\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eOverview of instrument parameters used for GD-SF-MS analysis.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"2\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePlasma voltage\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1000\u0026nbsp;V\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePlasma current\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e8\u0026nbsp;mA\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAr gas flow\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e450\u0026nbsp;mL\u0026nbsp;min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePulse duration\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e10\u0026nbsp;\u0026micro;s\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePulse frequency\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4\u0026nbsp;kHz\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCooling temperature\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0\u0026nbsp;\u0026deg;C\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAnode cap size\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e8\u0026nbsp;mm\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e "},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eConflict of Interest\u003c/h2\u003e \u003cp\u003eThe authors declare no conflict of interest.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor contributions\u003c/h2\u003e \u003cp\u003eConceptualization: S.L. Dorn; Methodology: S.L. Dorn (GD-SF-MS), J. Kauling (SEM-EDX, electrode preparation); Writing: S.L. Dorn; Review and editing: J. Kauling, M. B\u0026ouml;rner, M. Winter, S. Wiemers-Meyer, S. Nowak.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThe authors thank the German Federal Ministry of Education and Research (BMBF) for funding the project \u0026ldquo;BatGasMod\u0026rdquo; (03XP0311C). This work was additionally supported by the project 21GRD01 (OpMetBat), which received funding from the European Partnership on Metrology, cofinanced by the European Union\u0026rsquo;s Horizon Europe Research and Innovation Programme and by the Participating States. 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Surface analysis insight note: Illustrating the effect of adventitious contamination on Pt photoemission peak intensities. \u003cem\u003eSurface and Interface Analysis\u003c/em\u003e 56, 122\u0026ndash;125; \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1002/sia.7276\u003c/span\u003e\u003cspan address=\"10.1002/sia.7276\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e (2024).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Binder: Migration, LIBs, SF-GD-MS, Production","lastPublishedDoi":"10.21203/rs.3.rs-9449468/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9449468/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eA high amount of energy needed for the production of lithium ion batteries is used for the drying and solvent recovery of \u003cem\u003eN\u003c/em\u003e-methyl-2-pyrrolidone (NMP) in electrodes with polyvinylidene fluoride-based binder (PVdF) systems. Therefore, controlling the amount of used solvent as well as developing efficient drying procedures is of major importance. Furthermore, the drying process and solid content of the electrode paste directly affect the battery performance due to the risk of transport of the binder towards the electrode surface. This work focuses on an analytical approach for rapidly and reliably assessing the degree of this migration by measuring the fluorine distribution \u003cem\u003evia\u003c/em\u003e glow discharge-sector field-mass spectrometry (GD-SF-MS). A sample with notably more binder migration based on preliminary cross-section imaging \u003cem\u003evia\u003c/em\u003e scanning electron microscopy combined with energy-dispersive X-ray spectroscopy and a reference sample with no visualized binder migration were evaluated, with the former displaying a severely elevated degree of binder migration over the reference based on GD-SF-MS analysis. The developed method could also be applicable to electrodes based on sodium carboxymethyl cellulose (Na-CMC) binders by investigating the Na distribution instead.\u003c/p\u003e","manuscriptTitle":"Fast method for identifying and assessing binder migration in lithium ion battery electrodes via glow discharge-sector field-mass spectrometry","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-05-04 09:41:25","doi":"10.21203/rs.3.rs-9449468/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"communications-chemistry","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"commschem","sideBox":"Learn more about [Communications Chemistry](http://www.nature.com/commschem/)","snPcode":"","submissionUrl":"","title":"Communications Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Communications Series","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"544b0fad-6876-4ca9-965a-b4880ce975ab","owner":[],"postedDate":"May 4th, 2026","published":true,"recentEditorialEvents":[{"type":"editorInvitedReview","content":"This content is not available.","date":"2026-05-05T02:05:20+00:00","index":1,"fulltext":"This content is not available."}],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":66804248,"name":"Physical sciences/Materials science/Materials for energy and catalysis"},{"id":66804249,"name":"Physical sciences/Chemistry/Analytical chemistry/Mass spectrometry"}],"tags":[],"updatedAt":"2026-05-04T09:41:25+00:00","versionOfRecord":[],"versionCreatedAt":"2026-05-04 09:41:25","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-9449468","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-9449468","identity":"rs-9449468","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}