Structural and Na-ion conduction characteristics of Na3PSxSe4–x

doi:10.1039/c6ta03027k

Title: Structural and Na-ion conduction characteristics of Na ₃PS _xSe _4–x

The recent discovery of the isostructrual cubic Na ₃PS ₄ and Na ₃PSe ₄ as fast Na-ion conductors provided a general structural framework for the exploration of new sodium superionic conductors. In this work, we systematically investigated the structures and ionic conduction characteristics of a series of compounds with the general chemical formula of Na ₃PS _xSe _4–x. Synthesis of Na ₃PS ₄ under different conditions (e.g., temperature, reaction vessel, mass of the precursors) reveals the reactivity of the precursors with the reaction tubes, producing different polymorphs. X-ray diffraction studies on the solid solution phases Na ₃PS _xSe _4–x identified a tetragonal-to-cubic phase transition with increasing Se concentration. This observation is consistent with the computed stability of the tetragonal and cubic polymorphs, where the energy difference between the two polymorphs becomes very close to zero in Se-rich compositions. Furthermore, ab initio molecular dynamic simulations suggest that the fast Na-ion conduction in Na ₃PS _xSe _4–x may not be causally related with the symmetry or the composition of these phases. The formation of defects, instead, enables fast Na-ion conduction in this class of materials.

Authors:

Bo, Shou -Hang ^[1] ; Wang, Yan ^[2] ; Ceder, Gerbrand ^[3]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

Publication Date:: 2016-05-19

Grant/Contract Number:: AC02-05CH11231

Type:: Accepted Manuscript

Journal Name:: Journal of Materials Chemistry. A

Additional Journal Information:: Journal Volume: 4; Journal Issue: 23; Journal ID: ISSN 2050-7488

Publisher:: Royal Society of Chemistry

Research Org:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org:: USDOE Office of Science (SC)

Country of Publication:: United States

Language:: English

Subject:: 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

OSTI Identifier:: 1393007


                    Bo, Shou -Hang, Wang, Yan, and Ceder, Gerbrand. Structural and Na-ion conduction characteristics of Na3PSxSe4–x.  United States: N. p.,  
        Web.  doi:10.1039/c6ta03027k.

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                    Bo, Shou -Hang, Wang, Yan, & Ceder, Gerbrand. Structural and Na-ion conduction characteristics of Na3PSxSe4–x.  United States.  doi:10.1039/c6ta03027k.

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                    Bo, Shou -Hang, Wang, Yan, and Ceder, Gerbrand. 2016.  
        "Structural and Na-ion conduction characteristics of Na3PSxSe4–x".  United States.  
        doi:10.1039/c6ta03027k.  https://www.osti.gov/servlets/purl/1393007.

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@article{osti_1393007,

  title        = {Structural and Na-ion conduction characteristics of Na3PSxSe4–x},

  author       = {Bo, Shou -Hang and Wang, Yan and Ceder, Gerbrand},

  abstractNote = {The recent discovery of the isostructrual cubic Na3PS4 and Na3PSe4 as fast Na-ion conductors provided a general structural framework for the exploration of new sodium superionic conductors. In this work, we systematically investigated the structures and ionic conduction characteristics of a series of compounds with the general chemical formula of Na3PSxSe4–x. Synthesis of Na3PS4 under different conditions (e.g., temperature, reaction vessel, mass of the precursors) reveals the reactivity of the precursors with the reaction tubes, producing different polymorphs. X-ray diffraction studies on the solid solution phases Na3PSxSe4–x identified a tetragonal-to-cubic phase transition with increasing Se concentration. This observation is consistent with the computed stability of the tetragonal and cubic polymorphs, where the energy difference between the two polymorphs becomes very close to zero in Se-rich compositions. Furthermore, ab initio molecular dynamic simulations suggest that the fast Na-ion conduction in Na3PSxSe4–x may not be causally related with the symmetry or the composition of these phases. The formation of defects, instead, enables fast Na-ion conduction in this class of materials.},

  doi          = {10.1039/c6ta03027k},

  journal      = {Journal of Materials Chemistry. A},

  number       = 23,

  volume       = 4,

  place        = {United States},

  year         = {2016},

  month        = {5}

}

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10.1039/c6ta03027k
https://doi.org/10.1039/c6ta03027k

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
DOI: 10.1103/PhysRevLett.77.3865

Projector augmented-wave method
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Blöchl, P. E.
Physical Review B, Vol. 50, Issue 24, p. 17953-17979
DOI: 10.1103/PhysRevB.50.17953

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Kresse, G.; Furthmüller, J.
Physical Review B, Vol. 54, Issue 16, p. 11169-11186
DOI: 10.1103/PhysRevB.54.11169

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Title: Structural and Na-ion conduction characteristics of Na 3PS xSe 4–x

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Title: Structural and Na-ion conduction characteristics of Na ₃PS _xSe _4–x