A global design principle for polysulfide electrocatalysis in lithium–sulfur batteries—A computational perspective
Abstract Widespread commercialization of high‐energy‐density lithium–sulfur (Li–S) batteries is difficult due to the lithium polysulfide, Li2Sn (n = 4, 6, 8), shuttle effect. Efficient adsorption/conversion of Li2Sn species on an electrocatalytic surface can suppress the shuttle effect. Modeling of...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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Wiley
2022-07-01
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| Series: | Battery Energy |
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| Online Access: | https://doi.org/10.1002/bte2.20220003 |
| _version_ | 1811295216726966272 |
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| author | Akhil M. Abraham Thilini Boteju Sathish Ponnurangam Venkataraman Thangadurai |
| author_facet | Akhil M. Abraham Thilini Boteju Sathish Ponnurangam Venkataraman Thangadurai |
| author_sort | Akhil M. Abraham |
| collection | DOAJ |
| description | Abstract Widespread commercialization of high‐energy‐density lithium–sulfur (Li–S) batteries is difficult due to the lithium polysulfide, Li2Sn (n = 4, 6, 8), shuttle effect. Efficient adsorption/conversion of Li2Sn species on an electrocatalytic surface can suppress the shuttle effect. Modeling of the adsorption of Li2Sn species using density functional theory (DFT) calculations has contributed significantly toward an understanding of their anchoring mechanism at a surface. Different surfaces show a unique range of binding energies for faster Li2Sn adsorption/reaction kinetics. To predict the optimum binding energy zone, a systematic DFT study is performed on transition‐metal sulfide (TMS) surfaces including TiS2, VS2, NbS2, MoS2, WS2, and SnS2. The investigation revealed that the geometric properties at the anchoring site possibly regulate the adsorption energy of Li2Sn species. A geometry parameter, Gscore, is defined as a function of bond length and number of lithium‐atom interactions between the Li2Sn species and the binding surface. The design principle is extended to sulfur‐deficient (TMSs‐x) and edge‐exposed (TMS(100)) surfaces. The Gscore predicts the most effective binding energy zone distinctive to these materials—TMS (1.7–2.1 eV/Gscore ≥ 2.0), TMSs‐x (2.0–2.8 eV/Gscore ≥ 2.1), and TMS(100) (2.5–3.2 eV/Gscore ≥ 1.09). |
| first_indexed | 2024-04-13T05:29:14Z |
| format | Article |
| id | doaj.art-42679c4700984b8c896991476ad1f1ed |
| institution | Directory Open Access Journal |
| issn | 2768-1696 |
| language | English |
| last_indexed | 2024-04-13T05:29:14Z |
| publishDate | 2022-07-01 |
| publisher | Wiley |
| record_format | Article |
| series | Battery Energy |
| spelling | doaj.art-42679c4700984b8c896991476ad1f1ed2022-12-22T03:00:29ZengWileyBattery Energy2768-16962022-07-0113n/an/a10.1002/bte2.20220003A global design principle for polysulfide electrocatalysis in lithium–sulfur batteries—A computational perspectiveAkhil M. Abraham0Thilini Boteju1Sathish Ponnurangam2Venkataraman Thangadurai3Department of Chemistry University of Calgary Calgary Alberta CanadaDepartment of Chemistry University of Calgary Calgary Alberta CanadaDepartment of Chemical and Petroleum Engineering University of Calgary Calgary Alberta CanadaDepartment of Chemistry University of Calgary Calgary Alberta CanadaAbstract Widespread commercialization of high‐energy‐density lithium–sulfur (Li–S) batteries is difficult due to the lithium polysulfide, Li2Sn (n = 4, 6, 8), shuttle effect. Efficient adsorption/conversion of Li2Sn species on an electrocatalytic surface can suppress the shuttle effect. Modeling of the adsorption of Li2Sn species using density functional theory (DFT) calculations has contributed significantly toward an understanding of their anchoring mechanism at a surface. Different surfaces show a unique range of binding energies for faster Li2Sn adsorption/reaction kinetics. To predict the optimum binding energy zone, a systematic DFT study is performed on transition‐metal sulfide (TMS) surfaces including TiS2, VS2, NbS2, MoS2, WS2, and SnS2. The investigation revealed that the geometric properties at the anchoring site possibly regulate the adsorption energy of Li2Sn species. A geometry parameter, Gscore, is defined as a function of bond length and number of lithium‐atom interactions between the Li2Sn species and the binding surface. The design principle is extended to sulfur‐deficient (TMSs‐x) and edge‐exposed (TMS(100)) surfaces. The Gscore predicts the most effective binding energy zone distinctive to these materials—TMS (1.7–2.1 eV/Gscore ≥ 2.0), TMSs‐x (2.0–2.8 eV/Gscore ≥ 2.1), and TMS(100) (2.5–3.2 eV/Gscore ≥ 1.09).https://doi.org/10.1002/bte2.20220003anchoring mechanismdensity functional theory calculationslithium–sulfur batterytransition‐metal sulfidesRational Design of High‐Loading Sulfur Cathodes with a Poached‐Egg‐Shaped Architecture for Long‐Cycle Lithium−Sulfur Batteries |
| spellingShingle | Akhil M. Abraham Thilini Boteju Sathish Ponnurangam Venkataraman Thangadurai A global design principle for polysulfide electrocatalysis in lithium–sulfur batteries—A computational perspective Battery Energy anchoring mechanism density functional theory calculations lithium–sulfur battery transition‐metal sulfides Rational Design of High‐Loading Sulfur Cathodes with a Poached‐Egg‐Shaped Architecture for Long‐Cycle Lithium−Sulfur Batteries |
| title | A global design principle for polysulfide electrocatalysis in lithium–sulfur batteries—A computational perspective |
| title_full | A global design principle for polysulfide electrocatalysis in lithium–sulfur batteries—A computational perspective |
| title_fullStr | A global design principle for polysulfide electrocatalysis in lithium–sulfur batteries—A computational perspective |
| title_full_unstemmed | A global design principle for polysulfide electrocatalysis in lithium–sulfur batteries—A computational perspective |
| title_short | A global design principle for polysulfide electrocatalysis in lithium–sulfur batteries—A computational perspective |
| title_sort | global design principle for polysulfide electrocatalysis in lithium sulfur batteries a computational perspective |
| topic | anchoring mechanism density functional theory calculations lithium–sulfur battery transition‐metal sulfides Rational Design of High‐Loading Sulfur Cathodes with a Poached‐Egg‐Shaped Architecture for Long‐Cycle Lithium−Sulfur Batteries |
| url | https://doi.org/10.1002/bte2.20220003 |
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