Understanding lithiation induced volume variations and its impact on porous cobaltite (LiCo2O4) for Li-ion battery cathodes

Spinel LiCo2O4 exhibits superlative electrochemical performance due to its high Li+ diffusion rate; meanwhile, porous nanomaterials offer large surface areas and pore volume, allowing materials to expand freely with lithiation. However, it is very difficult to synthesise LiCo2O4 through conventional...

Full description

Saved in:
Bibliographic Details
Main Authors: L. Maake, B. Shibiri, P.E. Ngoepe, R.S. Ledwaba
Format: Article
Language:English
Published: Elsevier 2025-07-01
Series:Next Materials
Subjects:
Online Access:http://www.sciencedirect.com/science/article/pii/S2949822825001194
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1850207974915571712
author L. Maake
B. Shibiri
P.E. Ngoepe
R.S. Ledwaba
author_facet L. Maake
B. Shibiri
P.E. Ngoepe
R.S. Ledwaba
author_sort L. Maake
collection DOAJ
description Spinel LiCo2O4 exhibits superlative electrochemical performance due to its high Li+ diffusion rate; meanwhile, porous nanomaterials offer large surface areas and pore volume, allowing materials to expand freely with lithiation. However, it is very difficult to synthesise LiCo2O4 through conventional methods. As such, it has become redundant over the years. Therefore, herein, molecular dynamics simulation methods are employed to investigate the porosity and structural changes of three lithiated Li1+xCo2O4 (0 ≤ x ≤ 1) nanoporous materials with cell dimensions of 67, 69, and 75 Å during the discharge process to improve their cycling performance and structural stability. The radial distribution functions showed structures, which have sufficiently amorphised and recrystallised with lithiation. Furthermore, the simulated XRDs showed peaks that correspond to the formation of the cobaltite LiCo2O4 spinel when compared to experimental results. In addition, the XRDs also show significant peak shifts, splits, and broadening with increasing lithium concentration. This may be attributed to structural changes and phase transitions from cubic to tetragonal symmetry since multi-grained structures are observed at the Li1.75Co2O4 concentration. Pore size changes in the materials are also observed with increasing lithium concentration, and the nanoporous materials experience some volume changes during the discharge process. Nanoporous 69 Å material is observed to have a great overall volume increase compared to its counterparts. However, all the nanoporous materials retain their structural integrity upon full lithiation at Li2.00Co2O4; indicating their potential to enhance the cycling performance and structural stability of LiCo2O4 cathodes.
format Article
id doaj-art-b064e4db5d91401ea6db802f3de9e3a7
institution OA Journals
issn 2949-8228
language English
publishDate 2025-07-01
publisher Elsevier
record_format Article
series Next Materials
spelling doaj-art-b064e4db5d91401ea6db802f3de9e3a72025-08-20T02:10:20ZengElsevierNext Materials2949-82282025-07-01810060110.1016/j.nxmate.2025.100601Understanding lithiation induced volume variations and its impact on porous cobaltite (LiCo2O4) for Li-ion battery cathodesL. Maake0B. Shibiri1P.E. Ngoepe2R.S. Ledwaba3Corresponding author.; Materials Modelling Centre, University of Limpopo, Private Bag x 1106, Sovenga 0727, South AfricaMaterials Modelling Centre, University of Limpopo, Private Bag x 1106, Sovenga 0727, South AfricaMaterials Modelling Centre, University of Limpopo, Private Bag x 1106, Sovenga 0727, South AfricaMaterials Modelling Centre, University of Limpopo, Private Bag x 1106, Sovenga 0727, South AfricaSpinel LiCo2O4 exhibits superlative electrochemical performance due to its high Li+ diffusion rate; meanwhile, porous nanomaterials offer large surface areas and pore volume, allowing materials to expand freely with lithiation. However, it is very difficult to synthesise LiCo2O4 through conventional methods. As such, it has become redundant over the years. Therefore, herein, molecular dynamics simulation methods are employed to investigate the porosity and structural changes of three lithiated Li1+xCo2O4 (0 ≤ x ≤ 1) nanoporous materials with cell dimensions of 67, 69, and 75 Å during the discharge process to improve their cycling performance and structural stability. The radial distribution functions showed structures, which have sufficiently amorphised and recrystallised with lithiation. Furthermore, the simulated XRDs showed peaks that correspond to the formation of the cobaltite LiCo2O4 spinel when compared to experimental results. In addition, the XRDs also show significant peak shifts, splits, and broadening with increasing lithium concentration. This may be attributed to structural changes and phase transitions from cubic to tetragonal symmetry since multi-grained structures are observed at the Li1.75Co2O4 concentration. Pore size changes in the materials are also observed with increasing lithium concentration, and the nanoporous materials experience some volume changes during the discharge process. Nanoporous 69 Å material is observed to have a great overall volume increase compared to its counterparts. However, all the nanoporous materials retain their structural integrity upon full lithiation at Li2.00Co2O4; indicating their potential to enhance the cycling performance and structural stability of LiCo2O4 cathodes.http://www.sciencedirect.com/science/article/pii/S2949822825001194Nanoporous materialsMolecular dynamics simulationsAmorphisationRecrystallisationStructural stabilityVolume expansion
spellingShingle L. Maake
B. Shibiri
P.E. Ngoepe
R.S. Ledwaba
Understanding lithiation induced volume variations and its impact on porous cobaltite (LiCo2O4) for Li-ion battery cathodes
Next Materials
Nanoporous materials
Molecular dynamics simulations
Amorphisation
Recrystallisation
Structural stability
Volume expansion
title Understanding lithiation induced volume variations and its impact on porous cobaltite (LiCo2O4) for Li-ion battery cathodes
title_full Understanding lithiation induced volume variations and its impact on porous cobaltite (LiCo2O4) for Li-ion battery cathodes
title_fullStr Understanding lithiation induced volume variations and its impact on porous cobaltite (LiCo2O4) for Li-ion battery cathodes
title_full_unstemmed Understanding lithiation induced volume variations and its impact on porous cobaltite (LiCo2O4) for Li-ion battery cathodes
title_short Understanding lithiation induced volume variations and its impact on porous cobaltite (LiCo2O4) for Li-ion battery cathodes
title_sort understanding lithiation induced volume variations and its impact on porous cobaltite lico2o4 for li ion battery cathodes
topic Nanoporous materials
Molecular dynamics simulations
Amorphisation
Recrystallisation
Structural stability
Volume expansion
url http://www.sciencedirect.com/science/article/pii/S2949822825001194
work_keys_str_mv AT lmaake understandinglithiationinducedvolumevariationsanditsimpactonporouscobaltitelico2o4forliionbatterycathodes
AT bshibiri understandinglithiationinducedvolumevariationsanditsimpactonporouscobaltitelico2o4forliionbatterycathodes
AT pengoepe understandinglithiationinducedvolumevariationsanditsimpactonporouscobaltitelico2o4forliionbatterycathodes
AT rsledwaba understandinglithiationinducedvolumevariationsanditsimpactonporouscobaltitelico2o4forliionbatterycathodes