An inorganic-rich but LiF-free interphase for fast charging and long cycle life lithium metal batteries
Abstract Li metal batteries using Li metal as negative electrode and LiNi1-x-yMnxCoyO2 as positive electrode represent the next generation high-energy batteries. A major challenge facing these batteries is finding electrolytes capable of forming good interphases. Conventionally, electrolyte is fluor...
| Main Authors: | , , , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2023-12-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-44282-z |
| _version_ | 1827045292632965120 |
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| author | Muhammad Mominur Rahman Sha Tan Yang Yang Hui Zhong Sanjit Ghose Iradwikanari Waluyo Adrian Hunt Lu Ma Xiao-Qing Yang Enyuan Hu |
| author_facet | Muhammad Mominur Rahman Sha Tan Yang Yang Hui Zhong Sanjit Ghose Iradwikanari Waluyo Adrian Hunt Lu Ma Xiao-Qing Yang Enyuan Hu |
| author_sort | Muhammad Mominur Rahman |
| collection | DOAJ |
| description | Abstract Li metal batteries using Li metal as negative electrode and LiNi1-x-yMnxCoyO2 as positive electrode represent the next generation high-energy batteries. A major challenge facing these batteries is finding electrolytes capable of forming good interphases. Conventionally, electrolyte is fluorinated to generate anion-derived LiF-rich interphases. However, their low ionic conductivities forbid fast-charging. Here, we use CsNO3 as a dual-functional additive to form stable interphases on both electrodes. Such strategy allows the use of 1,2-dimethoxyethane as the single solvent, promising superior ion transport and fast charging. LiNi1-x-yMnxCoyO2 is protected by the nitrate-derived species. On the Li metal side, large Cs+ has weak interactions with the solvent, leading to presence of anions in the solvation sheath and an anion-derived interphase. The interphase is surprisingly dominated by cesium bis(fluorosulfonyl)imide, a component not reported before. Its presence suggests that Cs+ is doing more than just electrostatic shielding as commonly believed. The interphase is free of LiF but still promises high performance as cells with high LiNi0.8Mn0.1Co0.1O2 loading (21 mg/cm2) and low N/P ratio (~2) can be cycled at 2C (~8 mA/cm2) with above 80% capacity retention after 200 cycles. These results suggest the role of LiF and Cs-containing additives need to be revisited. |
| first_indexed | 2024-03-08T19:45:46Z |
| format | Article |
| id | doaj.art-c623c01fb3714276bc36e1157f542943 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2025-02-18T14:21:55Z |
| publishDate | 2023-12-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-c623c01fb3714276bc36e1157f5429432024-10-28T08:42:52ZengNature PortfolioNature Communications2041-17232023-12-0114111010.1038/s41467-023-44282-zAn inorganic-rich but LiF-free interphase for fast charging and long cycle life lithium metal batteriesMuhammad Mominur Rahman0Sha Tan1Yang Yang2Hui Zhong3Sanjit Ghose4Iradwikanari Waluyo5Adrian Hunt6Lu Ma7Xiao-Qing Yang8Enyuan Hu9Chemistry division, Brookhaven National LaboratoryChemistry division, Brookhaven National LaboratoryNational Synchrotron Lightsource II, Brookhaven National LaboratoryDepartment of Joint Photon Sciences Institute, Stony Brook UniversityNational Synchrotron Lightsource II, Brookhaven National LaboratoryNational Synchrotron Lightsource II, Brookhaven National LaboratoryNational Synchrotron Lightsource II, Brookhaven National LaboratoryNational Synchrotron Lightsource II, Brookhaven National LaboratoryChemistry division, Brookhaven National LaboratoryChemistry division, Brookhaven National LaboratoryAbstract Li metal batteries using Li metal as negative electrode and LiNi1-x-yMnxCoyO2 as positive electrode represent the next generation high-energy batteries. A major challenge facing these batteries is finding electrolytes capable of forming good interphases. Conventionally, electrolyte is fluorinated to generate anion-derived LiF-rich interphases. However, their low ionic conductivities forbid fast-charging. Here, we use CsNO3 as a dual-functional additive to form stable interphases on both electrodes. Such strategy allows the use of 1,2-dimethoxyethane as the single solvent, promising superior ion transport and fast charging. LiNi1-x-yMnxCoyO2 is protected by the nitrate-derived species. On the Li metal side, large Cs+ has weak interactions with the solvent, leading to presence of anions in the solvation sheath and an anion-derived interphase. The interphase is surprisingly dominated by cesium bis(fluorosulfonyl)imide, a component not reported before. Its presence suggests that Cs+ is doing more than just electrostatic shielding as commonly believed. The interphase is free of LiF but still promises high performance as cells with high LiNi0.8Mn0.1Co0.1O2 loading (21 mg/cm2) and low N/P ratio (~2) can be cycled at 2C (~8 mA/cm2) with above 80% capacity retention after 200 cycles. These results suggest the role of LiF and Cs-containing additives need to be revisited.https://doi.org/10.1038/s41467-023-44282-z |
| spellingShingle | Muhammad Mominur Rahman Sha Tan Yang Yang Hui Zhong Sanjit Ghose Iradwikanari Waluyo Adrian Hunt Lu Ma Xiao-Qing Yang Enyuan Hu An inorganic-rich but LiF-free interphase for fast charging and long cycle life lithium metal batteries Nature Communications |
| title | An inorganic-rich but LiF-free interphase for fast charging and long cycle life lithium metal batteries |
| title_full | An inorganic-rich but LiF-free interphase for fast charging and long cycle life lithium metal batteries |
| title_fullStr | An inorganic-rich but LiF-free interphase for fast charging and long cycle life lithium metal batteries |
| title_full_unstemmed | An inorganic-rich but LiF-free interphase for fast charging and long cycle life lithium metal batteries |
| title_short | An inorganic-rich but LiF-free interphase for fast charging and long cycle life lithium metal batteries |
| title_sort | inorganic rich but lif free interphase for fast charging and long cycle life lithium metal batteries |
| url | https://doi.org/10.1038/s41467-023-44282-z |
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