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Title: Nature of the “Z”-phase in layered Na-ion battery cathodes

Abstract

Layered sodium transition metal oxides with the P2 structure, e.g. Na2/3[Ni1/3Mn2/3]O2, are regarded as candidates for Na-ion battery cathodes. On charging, extraction of Na destabilizes the P2 phase (ABBA oxide ion stacking) in which Na+ is in trigonal prismatic coordination, resulting in layer gliding and formation of an O2 phase (ABAC stacking) with octahedral coordination. However, many related compounds do not exhibit such a simple P2 to O2 transition but rather form a so called “Z”-phase. Substituting Ni by Fe in Na2/3[Ni1/3Mn2/3]O2 is attractive as it reduces cost. The Fe containing compounds, such as Na2/3[Ni1/6Mn1/2Fe1/3]O2, form a “Z”-phase when charged above 4.1 V vs. Na+/Na. By combining ex situ and operando X-ray diffraction with scanning transmission electron microscopy and simulated diffraction patterns, we demonstrate that the “Z”-phase is most accurately described as a continuously changing intergrowth structure which evolves from P2 to O2 through the OP4 structure as an intermediate. On charging, Na+ removal results in O-type stacking faults within the P2 structure which increase in proportion. At 50% O-type stacking faults, the ordered OP4 phase forms and on further charging more O-type stacking faults are formed progressing towards a pure O2 structure. This gives the superficial appearance of amore » solid solution. Furthermore, in contrast to some previous studies, we did not detect Fe migration at any state-of-charge using 57Fe-Mössbauer spectroscopy. It was, however, found that the Fe-substitution serves to disrupt cation ordering in the material.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1]; ORCiD logo [3];  [4];  [4];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Dept. of Materials, University of Oxford, Parks Road, Oxford OX1 3PH, UK
  2. Paul Scherrer Institut, Electrochemical Laboratory, Switzerland
  3. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, USA
  4. Dept. of Chemistry, Ångstrom Lab., Uppsala University, Box 538, SE-751 21 Uppsala
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); The Faraday Institution; Engineering and Physical Sciences Research Council (EPSRC)
OSTI Identifier:
1513306
Alternate Identifier(s):
OSTI ID: 1560036
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Name: Energy & Environmental Science Journal Volume: 12 Journal Issue: 7; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE

Citation Formats

Somerville, James W., Sobkowiak, Adam, Tapia-Ruiz, Nuria, Billaud, Juliette, Lozano, Juan G., House, Robert A., Gallington, Leighanne C., Ericsson, Tore, Häggström, Lennart, Roberts, Matthew R., Maitra, Urmimala, and Bruce, Peter G. Nature of the “Z”-phase in layered Na-ion battery cathodes. United Kingdom: N. p., 2019. Web. doi:10.1039/C8EE02991A.
Somerville, James W., Sobkowiak, Adam, Tapia-Ruiz, Nuria, Billaud, Juliette, Lozano, Juan G., House, Robert A., Gallington, Leighanne C., Ericsson, Tore, Häggström, Lennart, Roberts, Matthew R., Maitra, Urmimala, & Bruce, Peter G. Nature of the “Z”-phase in layered Na-ion battery cathodes. United Kingdom. doi:10.1039/C8EE02991A.
Somerville, James W., Sobkowiak, Adam, Tapia-Ruiz, Nuria, Billaud, Juliette, Lozano, Juan G., House, Robert A., Gallington, Leighanne C., Ericsson, Tore, Häggström, Lennart, Roberts, Matthew R., Maitra, Urmimala, and Bruce, Peter G. Wed . "Nature of the “Z”-phase in layered Na-ion battery cathodes". United Kingdom. doi:10.1039/C8EE02991A.
@article{osti_1513306,
title = {Nature of the “Z”-phase in layered Na-ion battery cathodes},
author = {Somerville, James W. and Sobkowiak, Adam and Tapia-Ruiz, Nuria and Billaud, Juliette and Lozano, Juan G. and House, Robert A. and Gallington, Leighanne C. and Ericsson, Tore and Häggström, Lennart and Roberts, Matthew R. and Maitra, Urmimala and Bruce, Peter G.},
abstractNote = {Layered sodium transition metal oxides with the P2 structure, e.g. Na2/3[Ni1/3Mn2/3]O2, are regarded as candidates for Na-ion battery cathodes. On charging, extraction of Na destabilizes the P2 phase (ABBA oxide ion stacking) in which Na+ is in trigonal prismatic coordination, resulting in layer gliding and formation of an O2 phase (ABAC stacking) with octahedral coordination. However, many related compounds do not exhibit such a simple P2 to O2 transition but rather form a so called “Z”-phase. Substituting Ni by Fe in Na2/3[Ni1/3Mn2/3]O2 is attractive as it reduces cost. The Fe containing compounds, such as Na2/3[Ni1/6Mn1/2Fe1/3]O2, form a “Z”-phase when charged above 4.1 V vs. Na+/Na. By combining ex situ and operando X-ray diffraction with scanning transmission electron microscopy and simulated diffraction patterns, we demonstrate that the “Z”-phase is most accurately described as a continuously changing intergrowth structure which evolves from P2 to O2 through the OP4 structure as an intermediate. On charging, Na+ removal results in O-type stacking faults within the P2 structure which increase in proportion. At 50% O-type stacking faults, the ordered OP4 phase forms and on further charging more O-type stacking faults are formed progressing towards a pure O2 structure. This gives the superficial appearance of a solid solution. Furthermore, in contrast to some previous studies, we did not detect Fe migration at any state-of-charge using 57Fe-Mössbauer spectroscopy. It was, however, found that the Fe-substitution serves to disrupt cation ordering in the material.},
doi = {10.1039/C8EE02991A},
journal = {Energy & Environmental Science},
number = 7,
volume = 12,
place = {United Kingdom},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8EE02991A

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Cited by: 12 works
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Figures / Tables:

Figure S1 Figure S1: The P2, OP4, and O2 crystal structures projected parallel to the layers showing the stacking sequence.

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