{"title":"洞察气体分子吸附在二维-FeS2 上的影响:DFT 研究","authors":"Fen-Ning Zhao , Fu-Ling Tang , Hong-Tao Xue , Cheng-Dong Wei","doi":"10.1016/j.susc.2024.122509","DOIUrl":null,"url":null,"abstract":"<div><p>Lithium-sulfur (Li-S) batteries are especially competitive in the energy sector due to their excellent performances, like preferable energy density and economic benefits. Studying the adsorption of gas molecules on electrode materials has potential engineering significance for Li-S batteries since they have a highly osmotic potential, which causes unavoidable damage to batteries. In this work, the adsorption phenomenon of common gas molecules (H<sub>2</sub>O, N<sub>2</sub>, H<sub>2</sub>, CO<sub>2</sub>, and O<sub>2</sub>) on the two-dimensional pyrite (2D-FeS<sub>2</sub>) cathode material surface, as well as the effects on the electronic and electrochemical properties, were investigated by the first-principles calculations. The adsorption capabilities were estimated by adsorption energy and Mulliken population analysis. Simulation results demonstrated that whole adsorption energies were less than -1.0 eV and larger than -0.6 eV, which shows a physisorption nature. Among them, the O-S bond of O<sub>2</sub>/2D-FeS<sub>2</sub> has the strongest strength. Electronic structure calculations suggested that 2D-FeS<sub>2</sub> maintained good conductivity after gas molecules were adsorbed, achieving efficient transfer between electron, lithium, and sulfur intermediates. Additionally, <em>ab initio</em> molecular dynamics (AIMD) simulations showed that Li<sup>+</sup> exhibits excellent diffusion performance and low activation energy at different temperatures. 2D-FeS<sub>2</sub> still has a stable electrochemical working window (1.87 ∼ 2.47 V), while the theoretical open current voltage is damaged by gas molecule adsorption. Consequently, this work theoretically reveals the effect of gas molecules on the cathode materials for Li-S batteries, which has guide meaning for engineering.</p></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"747 ","pages":"Article 122509"},"PeriodicalIF":2.1000,"publicationDate":"2024-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Insight into the effects of gas molecules-adsorbed on 2D-FeS2: A DFT study\",\"authors\":\"Fen-Ning Zhao , Fu-Ling Tang , Hong-Tao Xue , Cheng-Dong Wei\",\"doi\":\"10.1016/j.susc.2024.122509\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Lithium-sulfur (Li-S) batteries are especially competitive in the energy sector due to their excellent performances, like preferable energy density and economic benefits. Studying the adsorption of gas molecules on electrode materials has potential engineering significance for Li-S batteries since they have a highly osmotic potential, which causes unavoidable damage to batteries. In this work, the adsorption phenomenon of common gas molecules (H<sub>2</sub>O, N<sub>2</sub>, H<sub>2</sub>, CO<sub>2</sub>, and O<sub>2</sub>) on the two-dimensional pyrite (2D-FeS<sub>2</sub>) cathode material surface, as well as the effects on the electronic and electrochemical properties, were investigated by the first-principles calculations. The adsorption capabilities were estimated by adsorption energy and Mulliken population analysis. Simulation results demonstrated that whole adsorption energies were less than -1.0 eV and larger than -0.6 eV, which shows a physisorption nature. Among them, the O-S bond of O<sub>2</sub>/2D-FeS<sub>2</sub> has the strongest strength. Electronic structure calculations suggested that 2D-FeS<sub>2</sub> maintained good conductivity after gas molecules were adsorbed, achieving efficient transfer between electron, lithium, and sulfur intermediates. Additionally, <em>ab initio</em> molecular dynamics (AIMD) simulations showed that Li<sup>+</sup> exhibits excellent diffusion performance and low activation energy at different temperatures. 2D-FeS<sub>2</sub> still has a stable electrochemical working window (1.87 ∼ 2.47 V), while the theoretical open current voltage is damaged by gas molecule adsorption. Consequently, this work theoretically reveals the effect of gas molecules on the cathode materials for Li-S batteries, which has guide meaning for engineering.</p></div>\",\"PeriodicalId\":22100,\"journal\":{\"name\":\"Surface Science\",\"volume\":\"747 \",\"pages\":\"Article 122509\"},\"PeriodicalIF\":2.1000,\"publicationDate\":\"2024-05-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Surface Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0039602824000608\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Surface Science","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0039602824000608","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Insight into the effects of gas molecules-adsorbed on 2D-FeS2: A DFT study
Lithium-sulfur (Li-S) batteries are especially competitive in the energy sector due to their excellent performances, like preferable energy density and economic benefits. Studying the adsorption of gas molecules on electrode materials has potential engineering significance for Li-S batteries since they have a highly osmotic potential, which causes unavoidable damage to batteries. In this work, the adsorption phenomenon of common gas molecules (H2O, N2, H2, CO2, and O2) on the two-dimensional pyrite (2D-FeS2) cathode material surface, as well as the effects on the electronic and electrochemical properties, were investigated by the first-principles calculations. The adsorption capabilities were estimated by adsorption energy and Mulliken population analysis. Simulation results demonstrated that whole adsorption energies were less than -1.0 eV and larger than -0.6 eV, which shows a physisorption nature. Among them, the O-S bond of O2/2D-FeS2 has the strongest strength. Electronic structure calculations suggested that 2D-FeS2 maintained good conductivity after gas molecules were adsorbed, achieving efficient transfer between electron, lithium, and sulfur intermediates. Additionally, ab initio molecular dynamics (AIMD) simulations showed that Li+ exhibits excellent diffusion performance and low activation energy at different temperatures. 2D-FeS2 still has a stable electrochemical working window (1.87 ∼ 2.47 V), while the theoretical open current voltage is damaged by gas molecule adsorption. Consequently, this work theoretically reveals the effect of gas molecules on the cathode materials for Li-S batteries, which has guide meaning for engineering.
期刊介绍:
Surface Science is devoted to elucidating the fundamental aspects of chemistry and physics occurring at a wide range of surfaces and interfaces and to disseminating this knowledge fast. The journal welcomes a broad spectrum of topics, including but not limited to:
• model systems (e.g. in Ultra High Vacuum) under well-controlled reactive conditions
• nanoscale science and engineering, including manipulation of matter at the atomic/molecular scale and assembly phenomena
• reactivity of surfaces as related to various applied areas including heterogeneous catalysis, chemistry at electrified interfaces, and semiconductors functionalization
• phenomena at interfaces relevant to energy storage and conversion, and fuels production and utilization
• surface reactivity for environmental protection and pollution remediation
• interactions at surfaces of soft matter, including polymers and biomaterials.
Both experimental and theoretical work, including modeling, is within the scope of the journal. Work published in Surface Science reaches a wide readership, from chemistry and physics to biology and materials science and engineering, providing an excellent forum for cross-fertilization of ideas and broad dissemination of scientific discoveries.