First-Principles Study on the Effect of Lithiation in Spinel Li<sub>x</sub>Mn<sub>2</sub>O<sub>4</sub> (0 ≤ x ≤ 1) Structure: Calibration of CASTEP and ONETEP Simulation Codes
Lithium–manganese–oxide (Li-Mn-O) spinel is among the promising and economically viable, high-energy density cathode materials for enhancing the performance of lithium-ion batteries. However, its commercialization is hindered by its poor cyclic performance. In computational modelling, pivotal in-dep...
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MDPI AG
2022-08-01
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| author | Donald Hlungwani Raesibe Sylvia Ledwaba Phuti Esrom Ngoepe |
| author_facet | Donald Hlungwani Raesibe Sylvia Ledwaba Phuti Esrom Ngoepe |
| author_sort | Donald Hlungwani |
| collection | DOAJ |
| description | Lithium–manganese–oxide (Li-Mn-O) spinel is among the promising and economically viable, high-energy density cathode materials for enhancing the performance of lithium-ion batteries. However, its commercialization is hindered by its poor cyclic performance. In computational modelling, pivotal in-depth understanding of material behaviour and properties is sizably propelled by advancements in computational methods. Hence, the current work compares traditional DFT (CASTEP) and linear-scaling DFT (ONETEP) in a LiMn<sub>2</sub>O<sub>4</sub> electronic property study to pave way for large-scale DFT calculations in a quest to improve its electrochemical properties. The metallic behaviour of Li<sub>x</sub>Mn<sub>2</sub>O<sub>4</sub> (0.25 ≤ x ≤ 1) and Li<sub>2</sub>Mn<sub>2</sub>O<sub>4</sub> was correctly determined by both CASTEP and ONETEP code in line with experiments. Furthermore, OCV during the discharge cycle deduced by both codes is in good accordance and is between 5 V and 2.5 V in the composition range of 0 ≤ x ≤ 1. Moreover, the scaling of the ONETEP code was performed at South Africa’s CHPC to provide guidelines on more productive large-scale ONETEP runs. Substantial total computing time can be saved by systematically adding the number of processors with the growing structure size. The study also substantiates that true linear scaling of the ONETEP code is achieved by a systematic truncation of the density kernel. |
| first_indexed | 2024-03-09T04:09:19Z |
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| institution | Directory Open Access Journal |
| issn | 1996-1944 |
| language | English |
| last_indexed | 2024-03-09T04:09:19Z |
| publishDate | 2022-08-01 |
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| spelling | doaj.art-0cbfce79496f4b9f9604d13b2a4ffd662023-12-03T14:02:06ZengMDPI AGMaterials1996-19442022-08-011516567810.3390/ma15165678First-Principles Study on the Effect of Lithiation in Spinel Li<sub>x</sub>Mn<sub>2</sub>O<sub>4</sub> (0 ≤ x ≤ 1) Structure: Calibration of CASTEP and ONETEP Simulation CodesDonald Hlungwani0Raesibe Sylvia Ledwaba1Phuti Esrom Ngoepe2Materials Modelling Centre, University of Limpopo, Private Bag X1106, Sovenga 0727, South AfricaMaterials Modelling Centre, University of Limpopo, Private Bag X1106, Sovenga 0727, South AfricaMaterials Modelling Centre, University of Limpopo, Private Bag X1106, Sovenga 0727, South AfricaLithium–manganese–oxide (Li-Mn-O) spinel is among the promising and economically viable, high-energy density cathode materials for enhancing the performance of lithium-ion batteries. However, its commercialization is hindered by its poor cyclic performance. In computational modelling, pivotal in-depth understanding of material behaviour and properties is sizably propelled by advancements in computational methods. Hence, the current work compares traditional DFT (CASTEP) and linear-scaling DFT (ONETEP) in a LiMn<sub>2</sub>O<sub>4</sub> electronic property study to pave way for large-scale DFT calculations in a quest to improve its electrochemical properties. The metallic behaviour of Li<sub>x</sub>Mn<sub>2</sub>O<sub>4</sub> (0.25 ≤ x ≤ 1) and Li<sub>2</sub>Mn<sub>2</sub>O<sub>4</sub> was correctly determined by both CASTEP and ONETEP code in line with experiments. Furthermore, OCV during the discharge cycle deduced by both codes is in good accordance and is between 5 V and 2.5 V in the composition range of 0 ≤ x ≤ 1. Moreover, the scaling of the ONETEP code was performed at South Africa’s CHPC to provide guidelines on more productive large-scale ONETEP runs. Substantial total computing time can be saved by systematically adding the number of processors with the growing structure size. The study also substantiates that true linear scaling of the ONETEP code is achieved by a systematic truncation of the density kernel.https://www.mdpi.com/1996-1944/15/16/5678LiMn<sub>2</sub>O<sub>4</sub>density functional theoryenergy storagelinear-scaling DFTlithium intercalationlithium-ion battery |
| spellingShingle | Donald Hlungwani Raesibe Sylvia Ledwaba Phuti Esrom Ngoepe First-Principles Study on the Effect of Lithiation in Spinel Li<sub>x</sub>Mn<sub>2</sub>O<sub>4</sub> (0 ≤ x ≤ 1) Structure: Calibration of CASTEP and ONETEP Simulation Codes Materials LiMn<sub>2</sub>O<sub>4</sub> density functional theory energy storage linear-scaling DFT lithium intercalation lithium-ion battery |
| title | First-Principles Study on the Effect of Lithiation in Spinel Li<sub>x</sub>Mn<sub>2</sub>O<sub>4</sub> (0 ≤ x ≤ 1) Structure: Calibration of CASTEP and ONETEP Simulation Codes |
| title_full | First-Principles Study on the Effect of Lithiation in Spinel Li<sub>x</sub>Mn<sub>2</sub>O<sub>4</sub> (0 ≤ x ≤ 1) Structure: Calibration of CASTEP and ONETEP Simulation Codes |
| title_fullStr | First-Principles Study on the Effect of Lithiation in Spinel Li<sub>x</sub>Mn<sub>2</sub>O<sub>4</sub> (0 ≤ x ≤ 1) Structure: Calibration of CASTEP and ONETEP Simulation Codes |
| title_full_unstemmed | First-Principles Study on the Effect of Lithiation in Spinel Li<sub>x</sub>Mn<sub>2</sub>O<sub>4</sub> (0 ≤ x ≤ 1) Structure: Calibration of CASTEP and ONETEP Simulation Codes |
| title_short | First-Principles Study on the Effect of Lithiation in Spinel Li<sub>x</sub>Mn<sub>2</sub>O<sub>4</sub> (0 ≤ x ≤ 1) Structure: Calibration of CASTEP and ONETEP Simulation Codes |
| title_sort | first principles study on the effect of lithiation in spinel li sub x sub mn sub 2 sub o sub 4 sub 0 ≤ x ≤ 1 structure calibration of castep and onetep simulation codes |
| topic | LiMn<sub>2</sub>O<sub>4</sub> density functional theory energy storage linear-scaling DFT lithium intercalation lithium-ion battery |
| url | https://www.mdpi.com/1996-1944/15/16/5678 |
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