Site-selective Mg-doping regulated charge storage in NaFe2PO4(SO4)2 for high energy sodium-ion batteries
Article
Pinjari, Sharad Dnyanu, Dutta, Ravi C., Chen, Shuimei, Mudavath, Purandas, Huang, Xiaodan, Bell, John, Bhatia, Suresh K., Nanjundan, Ashok Kumar and Gaddam, Rohit Ranganathan. 2024. "Site-selective Mg-doping regulated charge storage in NaFe2PO4(SO4)2 for high energy sodium-ion batteries." Chemical Engineering Journal. 493. https://doi.org/10.1016/j.cej.2024.152485
| Article Title | Site-selective Mg-doping regulated charge storage in NaFe2PO4(SO4)2 for high energy sodium-ion batteries |
|---|---|
| ERA Journal ID | 3854 |
| Article Category | Article |
| Authors | Pinjari, Sharad Dnyanu, Dutta, Ravi C., Chen, Shuimei, Mudavath, Purandas, Huang, Xiaodan, Bell, John, Bhatia, Suresh K., Nanjundan, Ashok Kumar and Gaddam, Rohit Ranganathan |
| Journal Title | Chemical Engineering Journal |
| Journal Citation | 493 |
| Article Number | 152485 |
| Number of Pages | 11 |
| Year | 2024 |
| Publisher | Elsevier |
| Place of Publication | Netherlands |
| ISSN | 1385-8947 |
| 1873-3212 | |
| Digital Object Identifier (DOI) | https://doi.org/10.1016/j.cej.2024.152485 |
| Web Address (URL) | https://www.sciencedirect.com/science/article/pii/S138589472403972X |
| Abstract | The absence of compatible cathodes with higher specific capacity and energy density hampers the full-scale commercial adaptation of sodium-ion batteries (NIB). Engineering NASICON cathodes with Fe redox centre and mixed polyanions is promising to overcome the bottlenecks. Our study uses a chemo-mechanical route to synthesise NaFe2−xMgxPO4(SO4)2 (NFMPS), where the dopant, Mg, is strategically positioned at the Fe sites. To our knowledge, such a chemo-mechanical synthesis of NASICON-type metal-phosphosulphate has not been attempted so far. Our work presents Mg2+ doping at the Fe site, in particular, for a NASICON-type NaFe2PO4(SO4)2 for the first time. With varying dopant concentrations, NFMPS is optimised to show a remarkable reversible capacity of around 111 mAh g−1 at C/20 with a corresponding energy density of 324 Wh kg−1. Even after 100 cycles at a C/5 current rate, the material retains 86.45 % of its initial capacity. An in-depth analysis of sodium-ion storage in NFMPS was conducted using electrochemical investigation, ex-situ characterisation methods and DFT calculations, where the presence of mixed polyanion and the dopant seem to enhance reversible sodium-ion (de)intercalation synergistically. DFT calculations indicate that the presence of Mg2+ can affect the localised electronic state of NFMPS and reduce the energy band gap of the material as evidenced from the electrical conductivity measurements for NFMPS. Ex-situ XRD studies at various (de)sodiation states showed that Mg-doping helps in retaining the material’s structural integrity and providing larger lattice sites for enhanced sodium-ion diffusion (ranging from 10−11 to 10−12 cm2 s−1). Higher working voltages, better sodium-ion transport, and capacity retention make NFMPS a promising candidate as a sodium-ion battery cathode. |
| Keywords | Cathodes; Sodium-ion battery ; Density functional theory ; NASICON; Chemomechanical synthesis |
| Contains Sensitive Content | Does not contain sensitive content |
| ANZSRC Field of Research 2020 | 400499. Chemical engineering not elsewhere classified |
| Byline Affiliations | Indian Institute of Science Education and Research Mohali (IISERM), India |
| Indian Institute of Technology Dharwad, India | |
| University of Queensland | |
| Office of the Deputy Vice-Chancellor (Research and Innovation) | |
| Centre for Future Materials | |
| School of Engineering |
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