Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub>
In our initial study on the high-voltage 5 V cobalt-free spinel LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> (LNMO) cathode, we discovered a severe delamination issue in the laminates when cycled at a high upper cut-off voltage (UCV) of 4.95 V, especially when...
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MDPI AG
2023-08-01
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| Online Access: | https://www.mdpi.com/2313-0105/9/9/435 |
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| author | Bingning Wang Seoung-Bum Son Pavan Badami Stephen E. Trask Daniel Abraham Yang Qin Zhenzhen Yang Xianyang Wu Andrew Jansen Chen Liao |
| author_facet | Bingning Wang Seoung-Bum Son Pavan Badami Stephen E. Trask Daniel Abraham Yang Qin Zhenzhen Yang Xianyang Wu Andrew Jansen Chen Liao |
| author_sort | Bingning Wang |
| collection | DOAJ |
| description | In our initial study on the high-voltage 5 V cobalt-free spinel LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> (LNMO) cathode, we discovered a severe delamination issue in the laminates when cycled at a high upper cut-off voltage (UCV) of 4.95 V, especially when a large cell format was used. This delamination problem prompted us to investigate further by studying the transition metal (TM) dissolution mechanism of cobalt-free LNMO cathodes, and as a comparison, some cobalt-containing lithium nickel manganese cobalt oxides (NMC) cathodes, as the leachates from the soaking experiment might be the culprit for the delamination. Unlike other previous reports, we are interested in the intrinsic stability of the cathode in the presence of a baseline Gen2 electrolyte consisting of 1.2 M of LiPF<sub>6</sub> in ethylene carbonate/ethyl methyl carbonate (EC/EMC), similar to a storage condition. The electrode laminates (transition metal oxides, transition metal oxides, TMOs, coated on an Al current collector with a loading level of around 2.5 mAh/cm<sup>2</sup>) or the TMO powders (pure commercial quality spinel LNMO, NMC, etc.) were stored in the baseline solution, and the transition metal dissolution was studied through nuclear magnetic resonance, such as <sup>1</sup>H NMR, <sup>19</sup>F NMR, scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS). Significant electrolyte decomposition was observed and could be the cause that leads to the TM dissolution of LNMO. To address this TM dissolution, additives were introduced into the baseline electrolyte, effectively alleviating the issue of TM dissolution. The results suggest that the observed delamination is caused by electrolyte decompositions that lead to etching, and additives such as lithium difluorooxalato borate and p-toluenesulfonyl isocyanate can alleviate this issue by forming a firm cathode electrolyte interface. This study provides a new perspective on cell degradation induced by electrode/electrolyte interactions under storage conditions. |
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| language | English |
| last_indexed | 2024-03-10T23:02:01Z |
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| spelling | doaj.art-0601f663d1ab49edb7c167493a0c0e122023-11-19T09:33:24ZengMDPI AGBatteries2313-01052023-08-019943510.3390/batteries9090435Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub>Bingning Wang0Seoung-Bum Son1Pavan Badami2Stephen E. Trask3Daniel Abraham4Yang Qin5Zhenzhen Yang6Xianyang Wu7Andrew Jansen8Chen Liao9Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, IL 60439, USAChemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, IL 60439, USAChemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, IL 60439, USAChemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, IL 60439, USAChemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, IL 60439, USADepartment of Chemical & Biomolecular Engineering, Institute of Materials Science, University of Connecticut, Storrs, CT 06269, USAChemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, IL 60439, USAChemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, IL 60439, USAChemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, IL 60439, USAChemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, IL 60439, USAIn our initial study on the high-voltage 5 V cobalt-free spinel LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> (LNMO) cathode, we discovered a severe delamination issue in the laminates when cycled at a high upper cut-off voltage (UCV) of 4.95 V, especially when a large cell format was used. This delamination problem prompted us to investigate further by studying the transition metal (TM) dissolution mechanism of cobalt-free LNMO cathodes, and as a comparison, some cobalt-containing lithium nickel manganese cobalt oxides (NMC) cathodes, as the leachates from the soaking experiment might be the culprit for the delamination. Unlike other previous reports, we are interested in the intrinsic stability of the cathode in the presence of a baseline Gen2 electrolyte consisting of 1.2 M of LiPF<sub>6</sub> in ethylene carbonate/ethyl methyl carbonate (EC/EMC), similar to a storage condition. The electrode laminates (transition metal oxides, transition metal oxides, TMOs, coated on an Al current collector with a loading level of around 2.5 mAh/cm<sup>2</sup>) or the TMO powders (pure commercial quality spinel LNMO, NMC, etc.) were stored in the baseline solution, and the transition metal dissolution was studied through nuclear magnetic resonance, such as <sup>1</sup>H NMR, <sup>19</sup>F NMR, scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS). Significant electrolyte decomposition was observed and could be the cause that leads to the TM dissolution of LNMO. To address this TM dissolution, additives were introduced into the baseline electrolyte, effectively alleviating the issue of TM dissolution. The results suggest that the observed delamination is caused by electrolyte decompositions that lead to etching, and additives such as lithium difluorooxalato borate and p-toluenesulfonyl isocyanate can alleviate this issue by forming a firm cathode electrolyte interface. This study provides a new perspective on cell degradation induced by electrode/electrolyte interactions under storage conditions.https://www.mdpi.com/2313-0105/9/9/435additivesdelaminationtransition metal dissolutionLiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub>soaking |
| spellingShingle | Bingning Wang Seoung-Bum Son Pavan Badami Stephen E. Trask Daniel Abraham Yang Qin Zhenzhen Yang Xianyang Wu Andrew Jansen Chen Liao Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> Batteries additives delamination transition metal dissolution LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> soaking |
| title | Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> |
| title_full | Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> |
| title_fullStr | Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> |
| title_full_unstemmed | Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> |
| title_short | Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> |
| title_sort | understanding and mitigating the dissolution and delamination issues encountered with high voltage lini sub 0 5 sub mn sub 1 5 sub o sub 4 sub |
| topic | additives delamination transition metal dissolution LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub> soaking |
| url | https://www.mdpi.com/2313-0105/9/9/435 |
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