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High voltage structural evolution and enhanced Na-ion diffusion in P2-Na2/3Ni1/3-xMgxMn2/3O2 (0 < x < 0.2) cathodes from diffraction, electrochemical and ab initio studies

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High voltage structural evolution and enhanced Na-ion diffusion in P2-Na2/3Ni1/3-xMgxMn2/3O2 (0 < x < 0.2) cathodes from diffraction, electrochemical and ab initio studies. / Tapia-Ruiz, Nuria; M. Dose, Wesley; Sharma, Neeraj; Chen, Hungru; Heath, Jennifer; Somerville, James W.; Maitra, Urmimala; Islam, M. Saiful; Bruce, Peter G.

In: Energy and Environmental Science, 16.03.2018.

Research output: Contribution to journalJournal articlepeer-review

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APA

Tapia-Ruiz, N., M. Dose, W., Sharma, N., Chen, H., Heath, J., Somerville, J. W., Maitra, U., Islam, M. S., & Bruce, P. G. (2018). High voltage structural evolution and enhanced Na-ion diffusion in P2-Na2/3Ni1/3-xMgxMn2/3O2 (0 < x < 0.2) cathodes from diffraction, electrochemical and ab initio studies. Energy and Environmental Science. https://doi.org/10.1039/C7EE02995K

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Author

Tapia-Ruiz, Nuria ; M. Dose, Wesley ; Sharma, Neeraj ; Chen, Hungru ; Heath, Jennifer ; Somerville, James W. ; Maitra, Urmimala ; Islam, M. Saiful ; Bruce, Peter G. / High voltage structural evolution and enhanced Na-ion diffusion in P2-Na2/3Ni1/3-xMgxMn2/3O2 (0 < x < 0.2) cathodes from diffraction, electrochemical and ab initio studies. In: Energy and Environmental Science. 2018.

Bibtex

@article{7850e998c4884d8c895cb99a74150d31,
title = "High voltage structural evolution and enhanced Na-ion diffusion in P2-Na2/3Ni1/3-xMgxMn2/3O2 (0 < x < 0.2) cathodes from diffraction, electrochemical and ab initio studies",
abstract = "We have presented a detailed investigation of the effects of Mg substitution on the structure, electrochemical performance and Na-ion diffusion in high voltage P2-type Na2/3Ni1/3-xMgxMn2/3O2 (0 <x< 0.20) cathode materials for Na-ion batteries. Structural analysis using neutron diffraction showed that Mg2+ substitutes random Ni2+ on the 2b sites from ordered [(Ni2+/Mn4+)O6] honeycomb units along the ab-plane, leading to an AB-type structure that can be indexed using the P63 space group. Within the sodium layers, high Mg-substituting levels (i.e. x = 0.2) caused a disruption in the typical Na zig-zag ordering observed in the undoped material, leading to a more disordered Na distribution in the layers. Load curves of the x = 0.1, 0.2 materials show smooth electrochemistry, indicative of a solid-solution process. Furthermore, DFT calculations showed an increase on Na-ion diffusivity on the Mg-substituted samples. Enhanced cycling stability was also observed in these materials; structural analysis using high-resolution in-operando synchrotron X-ray diffraction show that such an improved electrochemical performance is caused by the suppression of the O2 phase and switch to the formation of an OP4 phase. Ab-initio studies support our experimental evidence showing that the OP4 phase (cf. O2) is the most thermodynamically stable phase at high voltages for Mg-substituted compounds. Finally, we have provided evidence using diffraction for the x = 1/2 and x = 1/3 intermediate Na+-vacancy ordered phases in P2-Na 2/3Ni1/3Mn2/3O2.",
author = "Nuria Tapia-Ruiz and {M. Dose}, Wesley and Neeraj Sharma and Hungru Chen and Jennifer Heath and Somerville, {James W.} and Urmimala Maitra and Islam, {M. Saiful} and Bruce, {Peter G.}",
note = "{\textcopyright} Royal Society of Chemistry 2018",
year = "2018",
month = mar,
day = "16",
doi = "10.1039/C7EE02995K",
language = "English",
journal = "Energy and Environmental Science",
issn = "1754-5692",
publisher = "The Royal Society of Chemistry",

}

RIS

TY - JOUR

T1 - High voltage structural evolution and enhanced Na-ion diffusion in P2-Na2/3Ni1/3-xMgxMn2/3O2 (0 < x < 0.2) cathodes from diffraction, electrochemical and ab initio studies

AU - Tapia-Ruiz, Nuria

AU - M. Dose, Wesley

AU - Sharma, Neeraj

AU - Chen, Hungru

AU - Heath, Jennifer

AU - Somerville, James W.

AU - Maitra, Urmimala

AU - Islam, M. Saiful

AU - Bruce, Peter G.

N1 - © Royal Society of Chemistry 2018

PY - 2018/3/16

Y1 - 2018/3/16

N2 - We have presented a detailed investigation of the effects of Mg substitution on the structure, electrochemical performance and Na-ion diffusion in high voltage P2-type Na2/3Ni1/3-xMgxMn2/3O2 (0 <x< 0.20) cathode materials for Na-ion batteries. Structural analysis using neutron diffraction showed that Mg2+ substitutes random Ni2+ on the 2b sites from ordered [(Ni2+/Mn4+)O6] honeycomb units along the ab-plane, leading to an AB-type structure that can be indexed using the P63 space group. Within the sodium layers, high Mg-substituting levels (i.e. x = 0.2) caused a disruption in the typical Na zig-zag ordering observed in the undoped material, leading to a more disordered Na distribution in the layers. Load curves of the x = 0.1, 0.2 materials show smooth electrochemistry, indicative of a solid-solution process. Furthermore, DFT calculations showed an increase on Na-ion diffusivity on the Mg-substituted samples. Enhanced cycling stability was also observed in these materials; structural analysis using high-resolution in-operando synchrotron X-ray diffraction show that such an improved electrochemical performance is caused by the suppression of the O2 phase and switch to the formation of an OP4 phase. Ab-initio studies support our experimental evidence showing that the OP4 phase (cf. O2) is the most thermodynamically stable phase at high voltages for Mg-substituted compounds. Finally, we have provided evidence using diffraction for the x = 1/2 and x = 1/3 intermediate Na+-vacancy ordered phases in P2-Na 2/3Ni1/3Mn2/3O2.

AB - We have presented a detailed investigation of the effects of Mg substitution on the structure, electrochemical performance and Na-ion diffusion in high voltage P2-type Na2/3Ni1/3-xMgxMn2/3O2 (0 <x< 0.20) cathode materials for Na-ion batteries. Structural analysis using neutron diffraction showed that Mg2+ substitutes random Ni2+ on the 2b sites from ordered [(Ni2+/Mn4+)O6] honeycomb units along the ab-plane, leading to an AB-type structure that can be indexed using the P63 space group. Within the sodium layers, high Mg-substituting levels (i.e. x = 0.2) caused a disruption in the typical Na zig-zag ordering observed in the undoped material, leading to a more disordered Na distribution in the layers. Load curves of the x = 0.1, 0.2 materials show smooth electrochemistry, indicative of a solid-solution process. Furthermore, DFT calculations showed an increase on Na-ion diffusivity on the Mg-substituted samples. Enhanced cycling stability was also observed in these materials; structural analysis using high-resolution in-operando synchrotron X-ray diffraction show that such an improved electrochemical performance is caused by the suppression of the O2 phase and switch to the formation of an OP4 phase. Ab-initio studies support our experimental evidence showing that the OP4 phase (cf. O2) is the most thermodynamically stable phase at high voltages for Mg-substituted compounds. Finally, we have provided evidence using diffraction for the x = 1/2 and x = 1/3 intermediate Na+-vacancy ordered phases in P2-Na 2/3Ni1/3Mn2/3O2.

U2 - 10.1039/C7EE02995K

DO - 10.1039/C7EE02995K

M3 - Journal article

JO - Energy and Environmental Science

JF - Energy and Environmental Science

SN - 1754-5692

ER -