Ruo Wang , Jiawei Li , Bing Han , Qingrong Wang , Ruohong Ke , Tong Zhang , Xiaohu Ao , Guangzhao Zhang , Zhongbo Liu , Yunxian Qian , Fangfang Pan , Iseult Lynch , Jun Wang , Yonghong Deng
{"title":"采用氟化醚基电解质形成独特的双层固体电解质界面,用于高压锂金属电池","authors":"Ruo Wang , Jiawei Li , Bing Han , Qingrong Wang , Ruohong Ke , Tong Zhang , Xiaohu Ao , Guangzhao Zhang , Zhongbo Liu , Yunxian Qian , Fangfang Pan , Iseult Lynch , Jun Wang , Yonghong Deng","doi":"10.1016/j.jechem.2023.10.002","DOIUrl":null,"url":null,"abstract":"<div><p>Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density. However, they suffer from short lifespan and extreme safety concerns, which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage, as well as the high reactivity of metallic Li. The key is the development of stable electrolytes against both high-voltage cathodes and Li with the formation of robust interphase films on the surfaces. Herein, we report a highly fluorinated ether, 1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy) methoxy] ethane (TTME), as a co-solvent, which not only functions as a diluent forming a localized high concentration electrolyte (LHCE), but also participates in the construction of the inner solvation structure. The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase (SEI) film, which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility. The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28% after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm<sup>2</sup> and 1.0 mAh/cm<sup>2</sup>. In addition, lithium metal cells using LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> and LiCoO<sub>2</sub> cathodes (both loadings ∼3.0 mAh/cm<sup>2</sup>) realize capacity retentions of >85% over 240 cycles with a charge cut-off voltage of 4.4 V and 90% for 170 cycles with a charge cut-off voltage of 4.5 V, respectively. This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.</p></div>","PeriodicalId":67498,"journal":{"name":"能源化学","volume":"88 ","pages":"Pages 532-542"},"PeriodicalIF":14.0000,"publicationDate":"2023-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Unique double-layer solid electrolyte interphase formed with fluorinated ether-based electrolytes for high-voltage lithium metal batteries\",\"authors\":\"Ruo Wang , Jiawei Li , Bing Han , Qingrong Wang , Ruohong Ke , Tong Zhang , Xiaohu Ao , Guangzhao Zhang , Zhongbo Liu , Yunxian Qian , Fangfang Pan , Iseult Lynch , Jun Wang , Yonghong Deng\",\"doi\":\"10.1016/j.jechem.2023.10.002\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density. However, they suffer from short lifespan and extreme safety concerns, which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage, as well as the high reactivity of metallic Li. The key is the development of stable electrolytes against both high-voltage cathodes and Li with the formation of robust interphase films on the surfaces. Herein, we report a highly fluorinated ether, 1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy) methoxy] ethane (TTME), as a co-solvent, which not only functions as a diluent forming a localized high concentration electrolyte (LHCE), but also participates in the construction of the inner solvation structure. The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase (SEI) film, which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility. The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28% after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm<sup>2</sup> and 1.0 mAh/cm<sup>2</sup>. In addition, lithium metal cells using LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> and LiCoO<sub>2</sub> cathodes (both loadings ∼3.0 mAh/cm<sup>2</sup>) realize capacity retentions of >85% over 240 cycles with a charge cut-off voltage of 4.4 V and 90% for 170 cycles with a charge cut-off voltage of 4.5 V, respectively. This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.</p></div>\",\"PeriodicalId\":67498,\"journal\":{\"name\":\"能源化学\",\"volume\":\"88 \",\"pages\":\"Pages 532-542\"},\"PeriodicalIF\":14.0000,\"publicationDate\":\"2023-10-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"能源化学\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2095495623005582\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"能源化学","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2095495623005582","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Unique double-layer solid electrolyte interphase formed with fluorinated ether-based electrolytes for high-voltage lithium metal batteries
Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density. However, they suffer from short lifespan and extreme safety concerns, which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage, as well as the high reactivity of metallic Li. The key is the development of stable electrolytes against both high-voltage cathodes and Li with the formation of robust interphase films on the surfaces. Herein, we report a highly fluorinated ether, 1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy) methoxy] ethane (TTME), as a co-solvent, which not only functions as a diluent forming a localized high concentration electrolyte (LHCE), but also participates in the construction of the inner solvation structure. The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase (SEI) film, which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility. The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28% after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm2 and 1.0 mAh/cm2. In addition, lithium metal cells using LiNi0.8Co0.1Mn0.1O2 and LiCoO2 cathodes (both loadings ∼3.0 mAh/cm2) realize capacity retentions of >85% over 240 cycles with a charge cut-off voltage of 4.4 V and 90% for 170 cycles with a charge cut-off voltage of 4.5 V, respectively. This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.