Quantitative Lithiation Depth Profiling in Silicon Containing Anodes Investigated by Ion Beam Analysis
The localisation and quantitative analysis of lithium (Li) in battery materials, components, and full cells are scientifically highly relevant, yet challenging tasks. The methodical developments of MeV ion beam analysis (IBA) presented here open up new possibilities for simultaneous elemental quanti...
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| Format: | Article |
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MDPI AG
2022-02-01
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| Series: | Batteries |
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| Online Access: | https://www.mdpi.com/2313-0105/8/2/14 |
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| author | Sören Möller Hyunsang Joo Marcin Rasinski Markus Mann Egbert Figgemeier Martin Finsterbusch |
| author_facet | Sören Möller Hyunsang Joo Marcin Rasinski Markus Mann Egbert Figgemeier Martin Finsterbusch |
| author_sort | Sören Möller |
| collection | DOAJ |
| description | The localisation and quantitative analysis of lithium (Li) in battery materials, components, and full cells are scientifically highly relevant, yet challenging tasks. The methodical developments of MeV ion beam analysis (IBA) presented here open up new possibilities for simultaneous elemental quantification and localisation of light and heavy elements in Li and other batteries. It describes the technical prerequisites and limitations of using IBA to analyse and solve current challenges with the example of Li-ion and solid-state battery-related research and development. Here, nuclear reaction analysis and Rutherford backscattering spectrometry can provide spatial resolutions down to 70 nm and 1% accuracy. To demonstrate the new insights to be gained by IBA, SiO<sub>x</sub>-containing graphite anodes are lithiated to six states-of-charge (SoC) between 0–50%. The quantitative Li depth profiling of the anodes shows a linear increase of the Li concentration with SoC and a match of injected and detected Li-ions. This unambiguously proofs the electrochemical activity of Si. Already at 50% SoC, we derive C/Li = 5.4 (< LiC<sub>6</sub>) when neglecting Si, proving a relevant uptake of Li by the 8 atom % Si (C/Si ≈ 9) in the anode with Li/Si ≤ 1.8 in this case. Extrapolations to full lithiation show a maximum of Li/Si = 1.04 ± 0.05. The analysis reveals all element concentrations are constant over the anode thickness of 44 µm, except for a ~6-µm-thick separator-side surface layer. Here, the Li and Si concentrations are a factor 1.23 higher compared to the bulk for all SoC, indicating preferential Li binding to SiO<sub>x</sub>. These insights are so far not accessible with conventional analysis methods and are a first important step towards in-depth knowledge of quantitative Li distributions on the component level and a further application of IBA in the battery community. |
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| language | English |
| last_indexed | 2024-03-09T22:37:18Z |
| publishDate | 2022-02-01 |
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| series | Batteries |
| spelling | doaj.art-f9b75451f547411f96d6e2799797e3502023-11-23T18:47:31ZengMDPI AGBatteries2313-01052022-02-01821410.3390/batteries8020014Quantitative Lithiation Depth Profiling in Silicon Containing Anodes Investigated by Ion Beam AnalysisSören Möller0Hyunsang Joo1Marcin Rasinski2Markus Mann3Egbert Figgemeier4Martin Finsterbusch5Forschungszentrum Jülich GmbH, Institut für Energie und Klimaforschung, 52425 Jülich, GermanyHelmholtz Institute Münster (HI MS), IEK-12, Forschungszentrum Jülich GmbH, Jägerstr. 17–19, 52066 Aachen, GermanyForschungszentrum Jülich GmbH, Institut für Energie und Klimaforschung, 52425 Jülich, GermanyForschungszentrum Jülich GmbH, Institut für Energie und Klimaforschung, 52425 Jülich, GermanyHelmholtz Institute Münster (HI MS), IEK-12, Forschungszentrum Jülich GmbH, Jägerstr. 17–19, 52066 Aachen, GermanyForschungszentrum Jülich GmbH, Institut für Energie und Klimaforschung, 52425 Jülich, GermanyThe localisation and quantitative analysis of lithium (Li) in battery materials, components, and full cells are scientifically highly relevant, yet challenging tasks. The methodical developments of MeV ion beam analysis (IBA) presented here open up new possibilities for simultaneous elemental quantification and localisation of light and heavy elements in Li and other batteries. It describes the technical prerequisites and limitations of using IBA to analyse and solve current challenges with the example of Li-ion and solid-state battery-related research and development. Here, nuclear reaction analysis and Rutherford backscattering spectrometry can provide spatial resolutions down to 70 nm and 1% accuracy. To demonstrate the new insights to be gained by IBA, SiO<sub>x</sub>-containing graphite anodes are lithiated to six states-of-charge (SoC) between 0–50%. The quantitative Li depth profiling of the anodes shows a linear increase of the Li concentration with SoC and a match of injected and detected Li-ions. This unambiguously proofs the electrochemical activity of Si. Already at 50% SoC, we derive C/Li = 5.4 (< LiC<sub>6</sub>) when neglecting Si, proving a relevant uptake of Li by the 8 atom % Si (C/Si ≈ 9) in the anode with Li/Si ≤ 1.8 in this case. Extrapolations to full lithiation show a maximum of Li/Si = 1.04 ± 0.05. The analysis reveals all element concentrations are constant over the anode thickness of 44 µm, except for a ~6-µm-thick separator-side surface layer. Here, the Li and Si concentrations are a factor 1.23 higher compared to the bulk for all SoC, indicating preferential Li binding to SiO<sub>x</sub>. These insights are so far not accessible with conventional analysis methods and are a first important step towards in-depth knowledge of quantitative Li distributions on the component level and a further application of IBA in the battery community.https://www.mdpi.com/2313-0105/8/2/14all-solid-state batteriesgarnet solid-state electrolytelithium-ion transportelectrochemical stabilityion-beam analysisdepth-resolved analysis |
| spellingShingle | Sören Möller Hyunsang Joo Marcin Rasinski Markus Mann Egbert Figgemeier Martin Finsterbusch Quantitative Lithiation Depth Profiling in Silicon Containing Anodes Investigated by Ion Beam Analysis Batteries all-solid-state batteries garnet solid-state electrolyte lithium-ion transport electrochemical stability ion-beam analysis depth-resolved analysis |
| title | Quantitative Lithiation Depth Profiling in Silicon Containing Anodes Investigated by Ion Beam Analysis |
| title_full | Quantitative Lithiation Depth Profiling in Silicon Containing Anodes Investigated by Ion Beam Analysis |
| title_fullStr | Quantitative Lithiation Depth Profiling in Silicon Containing Anodes Investigated by Ion Beam Analysis |
| title_full_unstemmed | Quantitative Lithiation Depth Profiling in Silicon Containing Anodes Investigated by Ion Beam Analysis |
| title_short | Quantitative Lithiation Depth Profiling in Silicon Containing Anodes Investigated by Ion Beam Analysis |
| title_sort | quantitative lithiation depth profiling in silicon containing anodes investigated by ion beam analysis |
| topic | all-solid-state batteries garnet solid-state electrolyte lithium-ion transport electrochemical stability ion-beam analysis depth-resolved analysis |
| url | https://www.mdpi.com/2313-0105/8/2/14 |
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