{"title":"具有微调溶解结构的不可燃部分氟化电解质可实现宽温高电压钴酸锂电池","authors":"","doi":"10.1016/j.jechem.2024.10.007","DOIUrl":null,"url":null,"abstract":"<div><div>Efficient, safe, and reliable energy output from high-energy–density lithium metal batteries (LMBs) at all climates is crucial for portable electronic devices operating in complex environments. The performance of corresponding cathodes and lithium (Li) metal anodes, however, faces significant challenges under such demanding conditions. Herein, a nonflammable electrolyte for high-voltage Li||LCO cells has been designed, including partially-fluorinated ethyl 4,4,4-trifluorobutyrate (ETFB) as the key solvent, guided by theoretical calculations. With this ETFB-based electrolyte, Li||LCO cells exhibit enhanced reversible capacities and superior capacity retention at an elevated charge voltage of 4.5 V and a wide operating temperature range spanning from −60 °C to 70 °C. The cells achieve 67.1% discharge capacity at −60 °C, relative to room temperature capacity, and 85.9% 100th-cycle retention at 70 °C. The outstanding properties are attributed to the LiF-rich interphases formed in the ETFB-based electrolyte with a fine-tuned solvation structure, in which the coordination environment in the vicinity of Li<sup>+</sup> cations and the distance between anion and solvents are subtly adjusted by introducing ETFB. This solvation structure has been mutually elucidated through joint spectra characterizations and atomistic simulations. This work presents a new strategy for the design of electrolytes to achieve all-climate reliable and safe application of LMBs.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1000,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Wide-temperature and high-voltage Li||LiCoO2 cells enabled by a nonflammable partially-fluorinated electrolyte with fine-tuning solvation structure\",\"authors\":\"\",\"doi\":\"10.1016/j.jechem.2024.10.007\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Efficient, safe, and reliable energy output from high-energy–density lithium metal batteries (LMBs) at all climates is crucial for portable electronic devices operating in complex environments. The performance of corresponding cathodes and lithium (Li) metal anodes, however, faces significant challenges under such demanding conditions. Herein, a nonflammable electrolyte for high-voltage Li||LCO cells has been designed, including partially-fluorinated ethyl 4,4,4-trifluorobutyrate (ETFB) as the key solvent, guided by theoretical calculations. With this ETFB-based electrolyte, Li||LCO cells exhibit enhanced reversible capacities and superior capacity retention at an elevated charge voltage of 4.5 V and a wide operating temperature range spanning from −60 °C to 70 °C. The cells achieve 67.1% discharge capacity at −60 °C, relative to room temperature capacity, and 85.9% 100th-cycle retention at 70 °C. The outstanding properties are attributed to the LiF-rich interphases formed in the ETFB-based electrolyte with a fine-tuned solvation structure, in which the coordination environment in the vicinity of Li<sup>+</sup> cations and the distance between anion and solvents are subtly adjusted by introducing ETFB. This solvation structure has been mutually elucidated through joint spectra characterizations and atomistic simulations. This work presents a new strategy for the design of electrolytes to achieve all-climate reliable and safe application of LMBs.</div></div>\",\"PeriodicalId\":15728,\"journal\":{\"name\":\"Journal of Energy Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":13.1000,\"publicationDate\":\"2024-10-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Energy Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2095495624007009\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"Energy\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Energy Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2095495624007009","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"Energy","Score":null,"Total":0}
引用次数: 0
摘要
高能量密度锂金属电池(LMB)在任何气候条件下都能高效、安全、可靠地输出能量,这对于在复杂环境中工作的便携式电子设备至关重要。然而,在如此苛刻的条件下,相应阴极和锂(Li)金属阳极的性能面临着巨大挑战。在此,我们以理论计算为指导,设计了一种用于高压锂||LCO 电池的不可燃电解质,其中包括作为关键溶剂的部分氟化的 4,4,4-三氟丁酸乙酯(ETFB)。使用这种基于 ETFB 的电解质,锂||LCO 电池在 4.5 V 的较高充电电压和 -60 °C 至 70 °C 的较宽工作温度范围内,均表现出更强的可逆容量和出色的容量保持能力。相对于室温容量,电池在-60 °C时的放电容量达到67.1%,在70 °C时的第100次循环容量保持率达到85.9%。出色的性能归功于在基于 ETFB 的电解质中形成的富含 LiF 的相间,该电解质具有微调的溶解结构,通过引入 ETFB,Li+阳离子附近的配位环境以及阴离子与溶剂之间的距离都得到了微妙的调整。这种溶解结构是通过光谱特性分析和原子模拟共同阐明的。这项工作为电解质的设计提供了一种新策略,从而实现 LMB 在全气候条件下的可靠和安全应用。
Wide-temperature and high-voltage Li||LiCoO2 cells enabled by a nonflammable partially-fluorinated electrolyte with fine-tuning solvation structure
Efficient, safe, and reliable energy output from high-energy–density lithium metal batteries (LMBs) at all climates is crucial for portable electronic devices operating in complex environments. The performance of corresponding cathodes and lithium (Li) metal anodes, however, faces significant challenges under such demanding conditions. Herein, a nonflammable electrolyte for high-voltage Li||LCO cells has been designed, including partially-fluorinated ethyl 4,4,4-trifluorobutyrate (ETFB) as the key solvent, guided by theoretical calculations. With this ETFB-based electrolyte, Li||LCO cells exhibit enhanced reversible capacities and superior capacity retention at an elevated charge voltage of 4.5 V and a wide operating temperature range spanning from −60 °C to 70 °C. The cells achieve 67.1% discharge capacity at −60 °C, relative to room temperature capacity, and 85.9% 100th-cycle retention at 70 °C. The outstanding properties are attributed to the LiF-rich interphases formed in the ETFB-based electrolyte with a fine-tuned solvation structure, in which the coordination environment in the vicinity of Li+ cations and the distance between anion and solvents are subtly adjusted by introducing ETFB. This solvation structure has been mutually elucidated through joint spectra characterizations and atomistic simulations. This work presents a new strategy for the design of electrolytes to achieve all-climate reliable and safe application of LMBs.
期刊介绍:
The Journal of Energy Chemistry, the official publication of Science Press and the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, serves as a platform for reporting creative research and innovative applications in energy chemistry. It mainly reports on creative researches and innovative applications of chemical conversions of fossil energy, carbon dioxide, electrochemical energy and hydrogen energy, as well as the conversions of biomass and solar energy related with chemical issues to promote academic exchanges in the field of energy chemistry and to accelerate the exploration, research and development of energy science and technologies.
This journal focuses on original research papers covering various topics within energy chemistry worldwide, including:
Optimized utilization of fossil energy
Hydrogen energy
Conversion and storage of electrochemical energy
Capture, storage, and chemical conversion of carbon dioxide
Materials and nanotechnologies for energy conversion and storage
Chemistry in biomass conversion
Chemistry in the utilization of solar energy