Structural Investigation of Monoclinic‐Rhombohedral Phase Transition in Na 3 Zr 2 Si 2 PO 12 and Doped NASICON

Jolley, Adam G.; Taylor, Daniel D.; Schreiber, Nathaniel J.; Wachsman, Eric D.; Raveau, ed., B.

doi:10.1111/jace.13692

Title: Structural Investigation of Monoclinic‐Rhombohedral Phase Transition in Na ₃ Zr ₂ Si ₂ PO ₁₂ and Doped NASICON

Abstract

Aliovalent doping of the zirconium site in Na ₃ Zr ₂ Si ₂ PO ₁₂ ( NASICON ) was performed with a range of +3 (Al, Y, Fe) and +2 (Co, Ni, Zn) valent cations. The monoclinic‐rhombohedral phase transition was analyzed with high‐temperature in situ X‐ray diffraction, and differential scanning calorimetry ( DSC ). From the lattice parameters extracted at room temperature up to 300°C it was determined that the high‐temperature rhombohedral phase distorts to the low‐temperature monoclinic phase through a shear deformation of the unit cell. DSC confirmed the phase transition and demonstrated that the phase transition temperature was lowered by doping the NASICON structure. Furthermore, the distortion of the lattice was less severe for all doped samples. Ultimately aliovalent substitution for zirconium stabilized the higher symmetry rhombohedral phase of NASICON , with yttrium doping providing the lowest phase transition temperature and the smallest distortion of the lattice through the phase change.

Authors:

Jolley, Adam G. ^[1]; Taylor, Daniel D. ^[1]; Schreiber, Nathaniel J. ^[1]; Wachsman, Eric D. ^[1]; Raveau, ed., B.

University of Maryland Energy Research Center Department of Materials Science and Engineering University of Maryland, College Park Maryland 20742

Publication Date:: Thu Jun 18 00:00:00 EDT 2015

Sponsoring Org.:: USDOE

OSTI Identifier:: 1400713

Resource Type:: Publisher's Accepted Manuscript

Journal Name:: Journal of the American Ceramic Society

Additional Journal Information:: Journal Name: Journal of the American Ceramic Society Journal Volume: 98 Journal Issue: 9; Journal ID: ISSN 0002-7820

Publisher:: Wiley-Blackwell

Country of Publication:: United States

Language:: English

Citation Formats


                    Jolley, Adam G., Taylor, Daniel D., Schreiber, Nathaniel J., Wachsman, Eric D., and Raveau, ed., B. Structural Investigation of Monoclinic‐Rhombohedral Phase Transition in Na 3 Zr 2 Si 2 PO 12 and Doped NASICON.  United States: N. p., 2015. 
Web.  doi:10.1111/jace.13692.

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                    Jolley, Adam G., Taylor, Daniel D., Schreiber, Nathaniel J., Wachsman, Eric D., & Raveau, ed., B. Structural Investigation of Monoclinic‐Rhombohedral Phase Transition in Na 3 Zr 2 Si 2 PO 12 and Doped NASICON.  United States.  https://doi.org/10.1111/jace.13692

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                    Jolley, Adam G., Taylor, Daniel D., Schreiber, Nathaniel J., Wachsman, Eric D., and Raveau, ed., B. Thu .  
"Structural Investigation of Monoclinic‐Rhombohedral Phase Transition in Na 3 Zr 2 Si 2 PO 12 and Doped NASICON".  United States.  https://doi.org/10.1111/jace.13692.

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@article{osti_1400713,

  title        = {Structural Investigation of Monoclinic‐Rhombohedral Phase Transition in Na 3 Zr 2 Si 2 PO 12 and Doped NASICON},

  author       = {Jolley, Adam G. and Taylor, Daniel D. and Schreiber, Nathaniel J. and Wachsman, Eric D. and Raveau, ed., B.},

  abstractNote = {Aliovalent doping of the zirconium site in Na 3 Zr 2 Si 2 PO 12 ( NASICON ) was performed with a range of +3 (Al, Y, Fe) and +2 (Co, Ni, Zn) valent cations. The monoclinic‐rhombohedral phase transition was analyzed with high‐temperature in situ X‐ray diffraction, and differential scanning calorimetry ( DSC ). From the lattice parameters extracted at room temperature up to 300°C it was determined that the high‐temperature rhombohedral phase distorts to the low‐temperature monoclinic phase through a shear deformation of the unit cell. DSC confirmed the phase transition and demonstrated that the phase transition temperature was lowered by doping the NASICON structure. Furthermore, the distortion of the lattice was less severe for all doped samples. Ultimately aliovalent substitution for zirconium stabilized the higher symmetry rhombohedral phase of NASICON , with yttrium doping providing the lowest phase transition temperature and the smallest distortion of the lattice through the phase change.},

  doi          = {10.1111/jace.13692},

  journal      = {Journal of the American Ceramic Society},

  number       = 9,

  volume       = 98,

  place        = {United States},

  year         = {Thu Jun 18 00:00:00 EDT 2015},

  month        = {Thu Jun 18 00:00:00 EDT 2015}

}

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Works referenced in this record:

Superionic transitions in NASICON-type solid electrolytes
journal, January 1996

Bukun, N. G.
Ionics, Vol. 2, Issue 1
DOI: 10.1007/BF02375870

Crystal structures and crystal chemistry in the system Na1+xZr2SixP3−xO12
journal, February 1976

Hong, H. Y-P.
Materials Research Bulletin, Vol. 11, Issue 2
DOI: 10.1016/0025-5408(76)90073-8

Fast Na+-ion transport in skeleton structures
journal, February 1976

Goodenough, J. B.; Hong, H. Y-P.; Kafalas, J. A.
Materials Research Bulletin, Vol. 11, Issue 2
DOI: 10.1016/0025-5408(76)90077-5

Influence of microstructure on the electrical properties of NASICON materials
journal, March 2001

Fuentes, R.
Solid State Ionics, Vol. 140, Issue 1-2
DOI: 10.1016/S0167-2738(01)00701-9

Phase transition in nasicon (Na3Zr2Si2PO12)
journal, October 1979

von Alpen, U.; Bell, M. F.; Wichelhaus, W.
Materials Research Bulletin, Vol. 14, Issue 10
DOI: 10.1016/0025-5408(79)90010-2

Phase transition in, thermal history and expansion of NASICON, solid solution and lithium derivative ceramics and of SiC (mullite) fibers-NASICON composites
journal, November 1994

Colomban, P.; Mouchon, E.
Solid State Ionics, Vol. 73, Issue 3-4
DOI: 10.1016/0167-2738(94)90036-1

Orientational disorder, glass/crystal transition and superionic conductivity in nasicon
journal, September 1986

Colomban, P.
Solid State Ionics, Vol. 21, Issue 2
DOI: 10.1016/0167-2738(86)90201-8

Comparison of different synthesis methods for nasicon ceramics
journal, January 1995

Gasmi, N.; Gharbi, N.; Zarrouk, H.
Journal of Sol-Gel Science and Technology, Vol. 4, Issue 3
DOI: 10.1007/BF00488378

Compositional dependence of the electrochemical and structural parameters in the Nasicon system (Na1+xSixZr2P3−xO12)
journal, August 1981

Vonalpen, U.; Bell, M.; Hofer, H.
Solid State Ionics, Vol. 3-4
DOI: 10.1016/0167-2738(81)90085-0

Processing and electrical properties of NASICON prepared from yttria-doped zirconia precursors
journal, June 2001

Fuentes, R. O.; Figueiredo, F. M.; Marques, F. M. B.
Journal of the European Ceramic Society, Vol. 21, Issue 6
DOI: 10.1016/S0955-2219(00)00264-8

Sintering and characterization of alkaline-earth-doped and zirconium-defficient Na3Zr2Si2PO12
journal, September 1983

Lloyd, I. K.; Gupta, T. K.; Hall, B. O.
Solid State Ionics, Vol. 11, Issue 1
DOI: 10.1016/0167-2738(83)90060-7

Relation structure-fast ion conduction in the NASICON solid solution
journal, March 1988

Boilot, J. P.; Collin, G.; Colomban, Ph.
Journal of Solid State Chemistry, Vol. 73, Issue 1
DOI: 10.1016/0022-4596(88)90065-5

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Full Text Available
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Similar Records

Title: Structural Investigation of Monoclinic‐Rhombohedral Phase Transition in Na 3 Zr 2 Si 2 PO 12 and Doped NASICON

Abstract

Citation Formats

Superionic transitions in NASICON-type solid electrolytes journal, January 1996

Crystal structures and crystal chemistry in the system Na1+xZr2SixP3−xO12 journal, February 1976

Fast Na+-ion transport in skeleton structures journal, February 1976

Influence of microstructure on the electrical properties of NASICON materials journal, March 2001

Phase transition in nasicon (Na3Zr2Si2PO12) journal, October 1979

Phase transition in, thermal history and expansion of NASICON, solid solution and lithium derivative ceramics and of SiC (mullite) fibers-NASICON composites journal, November 1994

Orientational disorder, glass/crystal transition and superionic conductivity in nasicon journal, September 1986

Comparison of different synthesis methods for nasicon ceramics journal, January 1995

Compositional dependence of the electrochemical and structural parameters in the Nasicon system (Na1+xSixZr2P3−xO12) journal, August 1981

Processing and electrical properties of NASICON prepared from yttria-doped zirconia precursors journal, June 2001

Sintering and characterization of alkaline-earth-doped and zirconium-defficient Na3Zr2Si2PO12 journal, September 1983

Relation structure-fast ion conduction in the NASICON solid solution journal, March 1988

Title: Structural Investigation of Monoclinic‐Rhombohedral Phase Transition in Na ₃ Zr ₂ Si ₂ PO ₁₂ and Doped NASICON

Superionic transitions in NASICON-type solid electrolytes
journal, January 1996

Crystal structures and crystal chemistry in the system Na1+xZr2SixP3−xO12
journal, February 1976

Fast Na+-ion transport in skeleton structures
journal, February 1976

Influence of microstructure on the electrical properties of NASICON materials
journal, March 2001

Phase transition in nasicon (Na3Zr2Si2PO12)
journal, October 1979

Phase transition in, thermal history and expansion of NASICON, solid solution and lithium derivative ceramics and of SiC (mullite) fibers-NASICON composites
journal, November 1994

Orientational disorder, glass/crystal transition and superionic conductivity in nasicon
journal, September 1986

Comparison of different synthesis methods for nasicon ceramics
journal, January 1995

Compositional dependence of the electrochemical and structural parameters in the Nasicon system (Na1+xSixZr2P3−xO12)
journal, August 1981

Processing and electrical properties of NASICON prepared from yttria-doped zirconia precursors
journal, June 2001

Sintering and characterization of alkaline-earth-doped and zirconium-defficient Na3Zr2Si2PO12
journal, September 1983

Relation structure-fast ion conduction in the NASICON solid solution
journal, March 1988