{"title":"通过乙氧基(五氟)环三磷嗪电解质添加剂设计实现的自熄火高倍率氟化碳锂电池","authors":"","doi":"10.1016/j.nanoen.2024.110309","DOIUrl":null,"url":null,"abstract":"<div><div>The lithium/carbon fluoride (Li/CF<sub><em>x</em></sub>) battery has attracted significant attention due to its highest energy density among all commercially available lithium primary batteries. However, its high energy density also poses a significant risk during thermal runaway events, and its poor electrochemical performance at high discharge current densities limits its application in high-power devices. In this study, we propose a flame-retardant and interface-affinity enhancing electrolyte additive, ethoxy (pentafluoro) cyclotriphosphazene (PFPN), to regulate the electrolyte in Li/CF<sub><em>x</em></sub> batteries. The PFPN molecules participate in the lithium solvation shell, and its fluorine groups shows better affinity with the carbon fluoride cathode compared to traditional carbonate electrolytes. Furthermore, as a bulky molecule, PFPN reduces the desolvation energy of Li<sup>+</sup> ions after participating in lithium ion coordination, making it easier for Li<sup>+</sup> ions to be utilized at the carbon fluoride cathode, significantly enhancing the battery's rate performance. In a carbonate electrolyte containing 16 % PFPN additive (1 M LiBF<sub>4</sub>/EC+DMC, volume ratio 1:1), the CF<sub><em>x</em></sub> cathode delivers 277 % higher capacity at a current density of 1 A g<sup>−1</sup> compared to a CF<sub><em>x</em></sub> cathode without the additive. Additionally, due to the ability of PFPN to produce fluorine and phosphorus radicals at high temperatures that interrupt the combustion chain reaction, the electrolyte can achieve up to 10 instances of zero-second self-extinguishing, reducing the battery self-extinguishing time by 90 %. This study is the first to investigate the safety and flame-retardant electrolyte design of carbon fluoride batteries, providing a method to improve the power performance and safety of Li/CF<sub><em>x</em></sub> batteries at the same time.</div></div>","PeriodicalId":394,"journal":{"name":"Nano Energy","volume":null,"pages":null},"PeriodicalIF":16.8000,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A self fire-extinguishing and high rate lithium-fluorinated carbon battery realized by ethoxy (pentafluoro) cyclotriphosphazene electrolyte additive design\",\"authors\":\"\",\"doi\":\"10.1016/j.nanoen.2024.110309\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The lithium/carbon fluoride (Li/CF<sub><em>x</em></sub>) battery has attracted significant attention due to its highest energy density among all commercially available lithium primary batteries. However, its high energy density also poses a significant risk during thermal runaway events, and its poor electrochemical performance at high discharge current densities limits its application in high-power devices. In this study, we propose a flame-retardant and interface-affinity enhancing electrolyte additive, ethoxy (pentafluoro) cyclotriphosphazene (PFPN), to regulate the electrolyte in Li/CF<sub><em>x</em></sub> batteries. The PFPN molecules participate in the lithium solvation shell, and its fluorine groups shows better affinity with the carbon fluoride cathode compared to traditional carbonate electrolytes. Furthermore, as a bulky molecule, PFPN reduces the desolvation energy of Li<sup>+</sup> ions after participating in lithium ion coordination, making it easier for Li<sup>+</sup> ions to be utilized at the carbon fluoride cathode, significantly enhancing the battery's rate performance. In a carbonate electrolyte containing 16 % PFPN additive (1 M LiBF<sub>4</sub>/EC+DMC, volume ratio 1:1), the CF<sub><em>x</em></sub> cathode delivers 277 % higher capacity at a current density of 1 A g<sup>−1</sup> compared to a CF<sub><em>x</em></sub> cathode without the additive. Additionally, due to the ability of PFPN to produce fluorine and phosphorus radicals at high temperatures that interrupt the combustion chain reaction, the electrolyte can achieve up to 10 instances of zero-second self-extinguishing, reducing the battery self-extinguishing time by 90 %. This study is the first to investigate the safety and flame-retardant electrolyte design of carbon fluoride batteries, providing a method to improve the power performance and safety of Li/CF<sub><em>x</em></sub> batteries at the same time.</div></div>\",\"PeriodicalId\":394,\"journal\":{\"name\":\"Nano Energy\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":16.8000,\"publicationDate\":\"2024-09-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Nano Energy\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2211285524010619\",\"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":"Nano Energy","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2211285524010619","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}
A self fire-extinguishing and high rate lithium-fluorinated carbon battery realized by ethoxy (pentafluoro) cyclotriphosphazene electrolyte additive design
The lithium/carbon fluoride (Li/CFx) battery has attracted significant attention due to its highest energy density among all commercially available lithium primary batteries. However, its high energy density also poses a significant risk during thermal runaway events, and its poor electrochemical performance at high discharge current densities limits its application in high-power devices. In this study, we propose a flame-retardant and interface-affinity enhancing electrolyte additive, ethoxy (pentafluoro) cyclotriphosphazene (PFPN), to regulate the electrolyte in Li/CFx batteries. The PFPN molecules participate in the lithium solvation shell, and its fluorine groups shows better affinity with the carbon fluoride cathode compared to traditional carbonate electrolytes. Furthermore, as a bulky molecule, PFPN reduces the desolvation energy of Li+ ions after participating in lithium ion coordination, making it easier for Li+ ions to be utilized at the carbon fluoride cathode, significantly enhancing the battery's rate performance. In a carbonate electrolyte containing 16 % PFPN additive (1 M LiBF4/EC+DMC, volume ratio 1:1), the CFx cathode delivers 277 % higher capacity at a current density of 1 A g−1 compared to a CFx cathode without the additive. Additionally, due to the ability of PFPN to produce fluorine and phosphorus radicals at high temperatures that interrupt the combustion chain reaction, the electrolyte can achieve up to 10 instances of zero-second self-extinguishing, reducing the battery self-extinguishing time by 90 %. This study is the first to investigate the safety and flame-retardant electrolyte design of carbon fluoride batteries, providing a method to improve the power performance and safety of Li/CFx batteries at the same time.
期刊介绍:
Nano Energy is a multidisciplinary, rapid-publication forum of original peer-reviewed contributions on the science and engineering of nanomaterials and nanodevices used in all forms of energy harvesting, conversion, storage, utilization and policy. Through its mixture of articles, reviews, communications, research news, and information on key developments, Nano Energy provides a comprehensive coverage of this exciting and dynamic field which joins nanoscience and nanotechnology with energy science. The journal is relevant to all those who are interested in nanomaterials solutions to the energy problem.
Nano Energy publishes original experimental and theoretical research on all aspects of energy-related research which utilizes nanomaterials and nanotechnology. Manuscripts of four types are considered: review articles which inform readers of the latest research and advances in energy science; rapid communications which feature exciting research breakthroughs in the field; full-length articles which report comprehensive research developments; and news and opinions which comment on topical issues or express views on the developments in related fields.