Structure-electrochemical evolution of a Mn-rich P2 Na2/3Fe0.2Mn0.8O2 Na-ion battery cathode
Abstract
The structural evolution of electrode materials directly influences the performance of sodium-ion batteries. In this work, in situ synchrotron X-ray diffraction is used to investigate the evolution of the crystal structure of a Mn-rich P2-phase Na2/3Fe0.2Mn0.8O2 cathode. A single-phase reaction takes place for the majority of the discharge–charge cycle at ~C/10, with only a short, subtle hexagonal P2 to hexagonal P2 two-phase region early in the first charge. Thus, a higher fraction of Mn compared to previous studies is demonstrated to stabilize the P2 structure at high and low potentials, with neither “Z”/OP4 phases in the charged state nor significant quantities of the P'2 phase in the discharged state between 1.5 and 4.2 V. Notably, sodium ions inserted during discharge are located on both available crystallographic sites, albeit with a preference for the site sharing edges with the MO6 octahedral unit. The composition Na~0.70Fe0.2Mn0.8O2 prompts a reversible single-phase sodium redistribution between the two sites. Sodium ions vacate the site sharing faces (Naf), favoring the site sharing edges (Nae) to give a Nae/Naf site occupation of 4:1 in the discharged state. This site preference could be an intermediate state prior to the formation of the P'2 phase. Furthermore, this work showsmore »
- Authors:
-
- UNSW Sydney, Sydney, NSW (Australia); Argonne National Lab. (ANL), Argonne, IL (United States)
- UNSW Sydney, Sydney, NSW (Australia)
- UNSW Sydney, Sydney, NSW (Australia); Australia Nuclear Science and Technology Organisation, Kirrawee, DC NSW (Australia)
- Australian Synchrotron, Clayton, VIC (Australia)
- Parque Tecnologiva de Alava, Minano (Spain)
- Parque Tecnologiva de Alava, Minano (Spain); Univ. del Pais Vasco UPV/EHU, Bilbao (Spain)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- Spanish Ministerio de Economia y Competitividad (MINECO); University of New South Wales (UNSW); Australian Nuclear Science and Technology Organisation; Australian Institute of Nuclear Science and Engineering (AINSE); Australian Research Council; USDOE
- OSTI Identifier:
- 1393849
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 29; Journal Issue: 17; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; in situ synchrotron X-ray diffraction; positive electrodes; sodium site occupancy evolution; structure-function relationships
Citation Formats
Dose, Wesley M., Sharma, Neeraj, Pramudita, James C., Brand, Helen E. A., Gonzalo, Elena, and Rojo, Teofilo. Structure-electrochemical evolution of a Mn-rich P2 Na2/3Fe0.2Mn0.8O2 Na-ion battery cathode. United States: N. p., 2017.
Web. doi:10.1021/acs.chemmater.7b02397.
Dose, Wesley M., Sharma, Neeraj, Pramudita, James C., Brand, Helen E. A., Gonzalo, Elena, & Rojo, Teofilo. Structure-electrochemical evolution of a Mn-rich P2 Na2/3Fe0.2Mn0.8O2 Na-ion battery cathode. United States. https://doi.org/10.1021/acs.chemmater.7b02397
Dose, Wesley M., Sharma, Neeraj, Pramudita, James C., Brand, Helen E. A., Gonzalo, Elena, and Rojo, Teofilo. Fri .
"Structure-electrochemical evolution of a Mn-rich P2 Na2/3Fe0.2Mn0.8O2 Na-ion battery cathode". United States. https://doi.org/10.1021/acs.chemmater.7b02397. https://www.osti.gov/servlets/purl/1393849.
@article{osti_1393849,
title = {Structure-electrochemical evolution of a Mn-rich P2 Na2/3Fe0.2Mn0.8O2 Na-ion battery cathode},
author = {Dose, Wesley M. and Sharma, Neeraj and Pramudita, James C. and Brand, Helen E. A. and Gonzalo, Elena and Rojo, Teofilo},
abstractNote = {The structural evolution of electrode materials directly influences the performance of sodium-ion batteries. In this work, in situ synchrotron X-ray diffraction is used to investigate the evolution of the crystal structure of a Mn-rich P2-phase Na2/3Fe0.2Mn0.8O2 cathode. A single-phase reaction takes place for the majority of the discharge–charge cycle at ~C/10, with only a short, subtle hexagonal P2 to hexagonal P2 two-phase region early in the first charge. Thus, a higher fraction of Mn compared to previous studies is demonstrated to stabilize the P2 structure at high and low potentials, with neither “Z”/OP4 phases in the charged state nor significant quantities of the P'2 phase in the discharged state between 1.5 and 4.2 V. Notably, sodium ions inserted during discharge are located on both available crystallographic sites, albeit with a preference for the site sharing edges with the MO6 octahedral unit. The composition Na~0.70Fe0.2Mn0.8O2 prompts a reversible single-phase sodium redistribution between the two sites. Sodium ions vacate the site sharing faces (Naf), favoring the site sharing edges (Nae) to give a Nae/Naf site occupation of 4:1 in the discharged state. This site preference could be an intermediate state prior to the formation of the P'2 phase. Furthermore, this work shows how the Mn-rich Na2/3Fe0.2Mn0.8O2 composition and its sodium-ion distribution can minimize phase transitions during battery function, especially in the discharged state.},
doi = {10.1021/acs.chemmater.7b02397},
journal = {Chemistry of Materials},
number = 17,
volume = 29,
place = {United States},
year = {Fri Aug 04 00:00:00 EDT 2017},
month = {Fri Aug 04 00:00:00 EDT 2017}
}
Web of Science
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