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Nature of the "Z"-p...
Nature of the "Z"-phase in layered Na-ion battery cathodes
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- Somerville, James W. (författare)
- Univ Oxford, Dept Mat, Parks Rd, Oxford OX1 3PH, England
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- Sobkowiak, Adam (författare)
- Univ Oxford, Dept Mat, Parks Rd, Oxford OX1 3PH, England;Etteplan Sweden AB, SE-17154 Solna, Sweden
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- Tapia-Ruiz, Nuria (författare)
- Univ Oxford, Dept Mat, Parks Rd, Oxford OX1 3PH, England;Univ Lancaster, Dept Chem, Lancaster, England
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- Billaud, Juliette (författare)
- Paul Scherrer Inst, Electrochem Lab, CH-5232 Villigen, Switzerland
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- Lozano, Juan G. (författare)
- Univ Oxford, Dept Mat, Parks Rd, Oxford OX1 3PH, England;Univ Sevilla EPS US, Dept Ingn & Ciencia Mat & Transporte, Seville, Spain
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- House, Robert A. (författare)
- Univ Oxford, Dept Mat, Parks Rd, Oxford OX1 3PH, England
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- Gallington, Leighanne C. (författare)
- Argonne Natl Lab, Adv Photon Source, Xray Sci Div, Argonne, IL 60439 USA
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- Ericsson, Tore (författare)
- Uppsala universitet,Institutionen för kemi - Ångström
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- Häggström, Lennart (författare)
- Uppsala universitet,Institutionen för kemi - Ångström
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- Roberts, Matthew R. (författare)
- Univ Oxford, Dept Mat, Parks Rd, Oxford OX1 3PH, England
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- Maitra, Urmimala (författare)
- Univ Oxford, Dept Mat, Parks Rd, Oxford OX1 3PH, England;Justus Liebig Univ, Inst Phys Chem, Heinrich Buff Ring 17, D-35392 Giessen, Germany
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- Bruce, Peter G. (författare)
- Univ Oxford, Dept Mat, Parks Rd, Oxford OX1 3PH, England;Faraday Inst, Quad One,Becquerel Ave,Harwell Campus, Didcot OX11 0RA, Oxon, England
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(creator_code:org_t)
- 2019
- 2019
- Engelska.
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Ingår i: Energy & Environmental Science. - : ROYAL SOC CHEMISTRY. - 1754-5692 .- 1754-5706. ; 12:7, s. 2223-2232
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https://doi.org/10.1...
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https://uu.diva-port... (primary) (Raw object)
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https://pubs.rsc.org...
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
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- Layered sodium transition metal oxides with the P2 structure, e.g. Na-2/3[Ni1/3Mn2/3]O-2, 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 Na-2/3[Ni1/3Mn2/3]O-2 is attractive as it reduces cost. The Fe containing compounds, such as Na-2/3[Ni1/6Mn1/2Fe1/3]O-2, 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 Fe-57-Mossbauer spectroscopy. It was, however, found that the Fe-substitution serves to disrupt cation ordering in the material.
Ämnesord
- NATURVETENSKAP -- Kemi -- Oorganisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)
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Somerville, Jame ...
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Sobkowiak, Adam
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Tapia-Ruiz, Nuri ...
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Billaud, Juliett ...
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Lozano, Juan G.
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House, Robert A.
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Gallington, Leig ...
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Ericsson, Tore
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Häggström, Lenna ...
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Roberts, Matthew ...
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Maitra, Urmimala
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Bruce, Peter G.
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