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

Journal Article · · Energy & Environmental Science
DOI: https://doi.org/10.1039/c8ee02991a · OSTI ID:1513306
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 [5]
  1. Univ. of Oxford (United Kingdom)
  2. Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Uppsala Univ. (Sweden)
  5. Univ. of Oxford (United Kingdom); The Faraday Institution, Didcot (United Kingdom)
+ Show Author Affiliations

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC); The Faraday Institution; Engineering and Physical Sciences Research Council (EPSRC)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1513306
Alternate ID(s):
OSTI ID: 1560036
Journal Information:
Energy & Environmental Science, Vol. 12, Issue 7; ISSN 1754-5692
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 138 works
Citation information provided by
Web of Science

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Lead palladium titanate: A room temperature nanoscale multiferroic thin film journal February 2020

Cited By (3)

Effects of Mn‐Doping on the Structural and Electrochemical Properties of Na 3 Ni 2 SbO 6 for Sodium‐Ion Battery. journal January 2020
Rechargeable High‐Capacity Aluminum‐Nickel Batteries journal December 2019
Effects of Mn‐doping on the Structural and Electrochemical Properties of Na 3 Ni 2 SbO 6 for Sodium‐Ion Battery journal April 2020

Figures / Tables (9)

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