Investigating the Existence of a Cathode Electrolyte Interphase on Graphite in Dual‐Ion Batteries with LiPF6‐Based Aprotic Electrolytes and Unraveling the Origin of Capacity Fade
This study elucidates the presence of a cathode electrolyte interphase (CEI) at graphite positive electrodes (PEs) and assesses its impact on the performance of dual‐ion batteries, being promising candidates for cost‐efficient and sustainable stationary energy storage. Indeed, electrolyte oxidation...
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| Language: | English |
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Wiley-VCH
2025-03-01
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| Series: | Advanced Energy & Sustainability Research |
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| Online Access: | https://doi.org/10.1002/aesr.202400330 |
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| author | Lukas Haneke Felix Pfeiffer Katharina Rudolf Pranti Sutar Masoud Baghernejad Martin Winter Tobias Placke Johannes Kasnatscheew |
| author_facet | Lukas Haneke Felix Pfeiffer Katharina Rudolf Pranti Sutar Masoud Baghernejad Martin Winter Tobias Placke Johannes Kasnatscheew |
| author_sort | Lukas Haneke |
| collection | DOAJ |
| description | This study elucidates the presence of a cathode electrolyte interphase (CEI) at graphite positive electrodes (PEs) and assesses its impact on the performance of dual‐ion batteries, being promising candidates for cost‐efficient and sustainable stationary energy storage. Indeed, electrolyte oxidation increases during charge (5 V vs Li|Li+) for decreased C rates, that is longer duration at high state‐of‐charges (SOC) , but effective protection and evidence for CEI formation is missing as no increase in Coulombic efficiencies is observed, even with literature‐known electrolyte additives like vinylene carbonate, fluoroethylene carbonate, or ethylene sulfite in a highly concentrated base electrolyte (4.0 m LiPF6 in dimethyl carbonate) as reference. Via studying charged and pristine PEs by X‐ray photoelectron spectroscopy, PF6−‐graphite intercalation compounds and cointercalated solvent molecules are identified, while indications for CEI are absent within 1000 charge/discharge cycles. Nevertheless, a high capacity retention of ≈94% (referring to 0.1C) is demonstrated. Affirmed by Raman spectroscopy and scanning electron microscopy, the active material remains structurally stable, suggesting capacity fading to be dominated by resistance rise at the PE, likely due to an electronic contact resistance from active material grain boundaries and/or from the interface between electrode particles and the current collector in course of high volume changes; as systematically derived by impedance spectroscopy. |
| format | Article |
| id | doaj-art-4b6ade0e42a04b1893fbd3afaf9b8efd |
| institution | DOAJ |
| issn | 2699-9412 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | Wiley-VCH |
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| series | Advanced Energy & Sustainability Research |
| spelling | doaj-art-4b6ade0e42a04b1893fbd3afaf9b8efd2025-08-20T03:02:07ZengWiley-VCHAdvanced Energy & Sustainability Research2699-94122025-03-0163n/an/a10.1002/aesr.202400330Investigating the Existence of a Cathode Electrolyte Interphase on Graphite in Dual‐Ion Batteries with LiPF6‐Based Aprotic Electrolytes and Unraveling the Origin of Capacity FadeLukas Haneke0Felix Pfeiffer1Katharina Rudolf2Pranti Sutar3Masoud Baghernejad4Martin Winter5Tobias Placke6Johannes Kasnatscheew7MEET Battery Research Center Institute of Physical Chemistry University of Münster Corrensstraße 46 48149 Münster GermanyHelmholtz Institute Münster IEK‐12 Forschungszentrum Jülich GmbH Corrensstraße 46 48149 Münster GermanyMEET Battery Research Center Institute of Physical Chemistry University of Münster Corrensstraße 46 48149 Münster GermanyMEET Battery Research Center Institute of Physical Chemistry University of Münster Corrensstraße 46 48149 Münster GermanyHelmholtz Institute Münster IEK‐12 Forschungszentrum Jülich GmbH Corrensstraße 46 48149 Münster GermanyMEET Battery Research Center Institute of Physical Chemistry University of Münster Corrensstraße 46 48149 Münster GermanyMEET Battery Research Center Institute of Physical Chemistry University of Münster Corrensstraße 46 48149 Münster GermanyMEET Battery Research Center Institute of Physical Chemistry University of Münster Corrensstraße 46 48149 Münster GermanyThis study elucidates the presence of a cathode electrolyte interphase (CEI) at graphite positive electrodes (PEs) and assesses its impact on the performance of dual‐ion batteries, being promising candidates for cost‐efficient and sustainable stationary energy storage. Indeed, electrolyte oxidation increases during charge (5 V vs Li|Li+) for decreased C rates, that is longer duration at high state‐of‐charges (SOC) , but effective protection and evidence for CEI formation is missing as no increase in Coulombic efficiencies is observed, even with literature‐known electrolyte additives like vinylene carbonate, fluoroethylene carbonate, or ethylene sulfite in a highly concentrated base electrolyte (4.0 m LiPF6 in dimethyl carbonate) as reference. Via studying charged and pristine PEs by X‐ray photoelectron spectroscopy, PF6−‐graphite intercalation compounds and cointercalated solvent molecules are identified, while indications for CEI are absent within 1000 charge/discharge cycles. Nevertheless, a high capacity retention of ≈94% (referring to 0.1C) is demonstrated. Affirmed by Raman spectroscopy and scanning electron microscopy, the active material remains structurally stable, suggesting capacity fading to be dominated by resistance rise at the PE, likely due to an electronic contact resistance from active material grain boundaries and/or from the interface between electrode particles and the current collector in course of high volume changes; as systematically derived by impedance spectroscopy.https://doi.org/10.1002/aesr.202400330composite network resistanceselectrolyte oxidationelectronic versus ionic resistance risesgraphitic dual‐ion batteriessurface decomposition products |
| spellingShingle | Lukas Haneke Felix Pfeiffer Katharina Rudolf Pranti Sutar Masoud Baghernejad Martin Winter Tobias Placke Johannes Kasnatscheew Investigating the Existence of a Cathode Electrolyte Interphase on Graphite in Dual‐Ion Batteries with LiPF6‐Based Aprotic Electrolytes and Unraveling the Origin of Capacity Fade Advanced Energy & Sustainability Research composite network resistances electrolyte oxidation electronic versus ionic resistance rises graphitic dual‐ion batteries surface decomposition products |
| title | Investigating the Existence of a Cathode Electrolyte Interphase on Graphite in Dual‐Ion Batteries with LiPF6‐Based Aprotic Electrolytes and Unraveling the Origin of Capacity Fade |
| title_full | Investigating the Existence of a Cathode Electrolyte Interphase on Graphite in Dual‐Ion Batteries with LiPF6‐Based Aprotic Electrolytes and Unraveling the Origin of Capacity Fade |
| title_fullStr | Investigating the Existence of a Cathode Electrolyte Interphase on Graphite in Dual‐Ion Batteries with LiPF6‐Based Aprotic Electrolytes and Unraveling the Origin of Capacity Fade |
| title_full_unstemmed | Investigating the Existence of a Cathode Electrolyte Interphase on Graphite in Dual‐Ion Batteries with LiPF6‐Based Aprotic Electrolytes and Unraveling the Origin of Capacity Fade |
| title_short | Investigating the Existence of a Cathode Electrolyte Interphase on Graphite in Dual‐Ion Batteries with LiPF6‐Based Aprotic Electrolytes and Unraveling the Origin of Capacity Fade |
| title_sort | investigating the existence of a cathode electrolyte interphase on graphite in dual ion batteries with lipf6 based aprotic electrolytes and unraveling the origin of capacity fade |
| topic | composite network resistances electrolyte oxidation electronic versus ionic resistance rises graphitic dual‐ion batteries surface decomposition products |
| url | https://doi.org/10.1002/aesr.202400330 |
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