Peter M. Csernica, Kit McColl, Grace M. Busse, Kipil Lim, Diego F. Rivera, David A. Shapiro, M. Saiful Islam, William C. Chueh
{"title":"富锂层状氧化物在中度脱锂时的大量氧损耗和化学膨胀","authors":"Peter M. Csernica, Kit McColl, Grace M. Busse, Kipil Lim, Diego F. Rivera, David A. Shapiro, M. Saiful Islam, William C. Chueh","doi":"10.1038/s41563-024-02032-6","DOIUrl":null,"url":null,"abstract":"<p>Delithiation of layered oxide electrodes triggers irreversible oxygen loss, one of the primary degradation modes in lithium-ion batteries. However, the delithiation-dependent mechanisms of oxygen loss remain poorly understood. Here we investigate the oxygen non-stoichiometry in Li<sub>1.18–<i>x</i></sub>Ni<sub>0.21</sub>Mn<sub>0.53</sub>Co<sub>0.08</sub>O<sub>2–<i>δ</i></sub> electrodes as a function of Li content by using cycling protocols with long open-circuit voltage steps at varying states of charge. Surprisingly, we observe substantial oxygen loss even at moderate delithiation, corresponding to 2.5, 4.0 and 7.6 ml O<sub>2</sub> per gram of Li<sub>1.18–<i>x</i></sub>Ni<sub>0.21</sub>Mn<sub>0.53</sub>Co<sub>0.08</sub>O<sub>2–<i>δ</i></sub> after resting at upper capacity cut-offs of 135, 200 and 265 mAh g<sup>−1</sup> for 100 h. Our observations suggest an intrinsic oxygen instability consistent with predictions of high oxygen activity at intermediate potentials versus Li/Li<sup>+</sup>. In addition, we observe a large chemical expansion coefficient with respect to oxygen non-stoichiometry, which is about three times greater than those of classical oxygen-deficient materials such as fluorite and perovskite oxides. Our work challenges the conventional wisdom that deep delithiation is a necessary condition for oxygen loss in layered oxide electrodes and highlights the importance of calendar ageing for investigating oxygen stability.</p>","PeriodicalId":19058,"journal":{"name":"Nature Materials","volume":null,"pages":null},"PeriodicalIF":37.2000,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Substantial oxygen loss and chemical expansion in lithium-rich layered oxides at moderate delithiation\",\"authors\":\"Peter M. Csernica, Kit McColl, Grace M. Busse, Kipil Lim, Diego F. Rivera, David A. Shapiro, M. Saiful Islam, William C. Chueh\",\"doi\":\"10.1038/s41563-024-02032-6\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Delithiation of layered oxide electrodes triggers irreversible oxygen loss, one of the primary degradation modes in lithium-ion batteries. However, the delithiation-dependent mechanisms of oxygen loss remain poorly understood. Here we investigate the oxygen non-stoichiometry in Li<sub>1.18–<i>x</i></sub>Ni<sub>0.21</sub>Mn<sub>0.53</sub>Co<sub>0.08</sub>O<sub>2–<i>δ</i></sub> electrodes as a function of Li content by using cycling protocols with long open-circuit voltage steps at varying states of charge. Surprisingly, we observe substantial oxygen loss even at moderate delithiation, corresponding to 2.5, 4.0 and 7.6 ml O<sub>2</sub> per gram of Li<sub>1.18–<i>x</i></sub>Ni<sub>0.21</sub>Mn<sub>0.53</sub>Co<sub>0.08</sub>O<sub>2–<i>δ</i></sub> after resting at upper capacity cut-offs of 135, 200 and 265 mAh g<sup>−1</sup> for 100 h. Our observations suggest an intrinsic oxygen instability consistent with predictions of high oxygen activity at intermediate potentials versus Li/Li<sup>+</sup>. In addition, we observe a large chemical expansion coefficient with respect to oxygen non-stoichiometry, which is about three times greater than those of classical oxygen-deficient materials such as fluorite and perovskite oxides. Our work challenges the conventional wisdom that deep delithiation is a necessary condition for oxygen loss in layered oxide electrodes and highlights the importance of calendar ageing for investigating oxygen stability.</p>\",\"PeriodicalId\":19058,\"journal\":{\"name\":\"Nature Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":37.2000,\"publicationDate\":\"2024-10-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Nature Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1038/s41563-024-02032-6\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Nature Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1038/s41563-024-02032-6","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Substantial oxygen loss and chemical expansion in lithium-rich layered oxides at moderate delithiation
Delithiation of layered oxide electrodes triggers irreversible oxygen loss, one of the primary degradation modes in lithium-ion batteries. However, the delithiation-dependent mechanisms of oxygen loss remain poorly understood. Here we investigate the oxygen non-stoichiometry in Li1.18–xNi0.21Mn0.53Co0.08O2–δ electrodes as a function of Li content by using cycling protocols with long open-circuit voltage steps at varying states of charge. Surprisingly, we observe substantial oxygen loss even at moderate delithiation, corresponding to 2.5, 4.0 and 7.6 ml O2 per gram of Li1.18–xNi0.21Mn0.53Co0.08O2–δ after resting at upper capacity cut-offs of 135, 200 and 265 mAh g−1 for 100 h. Our observations suggest an intrinsic oxygen instability consistent with predictions of high oxygen activity at intermediate potentials versus Li/Li+. In addition, we observe a large chemical expansion coefficient with respect to oxygen non-stoichiometry, which is about three times greater than those of classical oxygen-deficient materials such as fluorite and perovskite oxides. Our work challenges the conventional wisdom that deep delithiation is a necessary condition for oxygen loss in layered oxide electrodes and highlights the importance of calendar ageing for investigating oxygen stability.
期刊介绍:
Nature Materials is a monthly multi-disciplinary journal aimed at bringing together cutting-edge research across the entire spectrum of materials science and engineering. It covers all applied and fundamental aspects of the synthesis/processing, structure/composition, properties, and performance of materials. The journal recognizes that materials research has an increasing impact on classical disciplines such as physics, chemistry, and biology.
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