Review Topical Sections

Phase relations of NASICON materials and compilation of the quaternary phase diagram Na2O-P2O5-SiO2-ZrO2

  • Received: 19 October 2017 Accepted: 28 November 2017 Published: 08 December 2017
  • A short overview is given on existing phase relations in the four related ternary diagrams, setting the frame for a quaternary phase diagram. On the basis of published data the three-dimensional phase region of NASICON materials is constructed and phase relations to ternary and binary systems as well as to single oxides are presented. To date, the NASICON region can be described as a compressed tetrahedron within the tetrahedral phase diagram. However, the three-dimensional presentation clearly elucidates that few reported compositions exist outside this compressed tetrahedron indicating that the phase region of NASICON materials may be larger than the solid solutions known so far. The three-dimensional representation also better elucidates the regions connecting the edges of the NASICON tetrahedron with ternary and binary compounds as well as single oxides, i.e., ZrO2 and ZrSiO4, Na3PO4, sodium silicates and sodium zirconium silicates and gives a better understanding of phase formations during the processing of the ceramics. The implications of the formation of secondary phases and glass-ceramic composites are discussed in terms of technological applications.

    Citation: Frank Tietz. Phase relations of NASICON materials and compilation of the quaternary phase diagram Na2O-P2O5-SiO2-ZrO2[J]. AIMS Materials Science, 2017, 4(6): 1305-1318. doi: 10.3934/matersci.2017.6.1305

    Related Papers:

  • A short overview is given on existing phase relations in the four related ternary diagrams, setting the frame for a quaternary phase diagram. On the basis of published data the three-dimensional phase region of NASICON materials is constructed and phase relations to ternary and binary systems as well as to single oxides are presented. To date, the NASICON region can be described as a compressed tetrahedron within the tetrahedral phase diagram. However, the three-dimensional presentation clearly elucidates that few reported compositions exist outside this compressed tetrahedron indicating that the phase region of NASICON materials may be larger than the solid solutions known so far. The three-dimensional representation also better elucidates the regions connecting the edges of the NASICON tetrahedron with ternary and binary compounds as well as single oxides, i.e., ZrO2 and ZrSiO4, Na3PO4, sodium silicates and sodium zirconium silicates and gives a better understanding of phase formations during the processing of the ceramics. The implications of the formation of secondary phases and glass-ceramic composites are discussed in terms of technological applications.


    加载中
    [1] Larcher D, Tarascon JM (2015) Towards greener and more sustainable batteries for electrical energy storage. Nat Chem 7: 19–29.
    [2] Doughty DH, Butler PC, Akhil AA, et al. (2010) Batteries for Large-Scale Stationary Electrical Energy Storage. Electrochem Soc Interface 19: 49–53.
    [3] Benato R, Cosciani N, Crugnola G, et al. (2015) Sodium nickel chloride battery technology for large-scale stationary storage in the high voltage network. J Power Sources 293: 127–136. doi: 10.1016/j.jpowsour.2015.05.037
    [4] Lu X, Xia G, Lemmon JP, et al. (2010) Advanced materials for sodium-beta alumina batteries: Status, challenges and perspectives. J Power Sources 195: 2431–2442. doi: 10.1016/j.jpowsour.2009.11.120
    [5] Hong HYP (1976) Crystal Structure and Crystal Chemistry in the System Na1+xZr2SixP3−xO12. Mater Res Bull 11: 173–182. doi: 10.1016/0025-5408(76)90073-8
    [6] Goodenough JB, Hong HYP, Kafalas JA (1976) Fast Na+-Ion Transport in Skeleton Structures. Mater Res Bull 11: 203–220. doi: 10.1016/0025-5408(76)90077-5
    [7] Kim J, Jo SH, Bhavaraju S, et al. (2015) Low temperature performance of sodium–nickel chloride batteries with NaSICON solid electrolyte. J Electroanal Chem 759: 201–206. doi: 10.1016/j.jelechem.2015.11.022
    [8] May GJ, Hooper A (1978) The effect of microstructure and phase composition on the ionic conductivity of magnesium-doped sodium-beta-alumina. J Mater Sci 13: 1480–1486. doi: 10.1007/BF00553202
    [9] Clearfield A, Guerra R, Oskarsson A, et al. (1983) Preparation of Sodium Zirconium Phosphates of the Type Na1+4xZr2−x(PO4)3. Mater Res Bull 18: 1561–1567. doi: 10.1016/0025-5408(83)90198-8
    [10] von Alpen U, Bell MF, Höfer HH (1981) Compositional Dependence of the Electrochemical and Structural Parameters in the NASICON System (Na1+xSixZr2P3−xO12). Solid State Ionics 3–4: 215–218.
    [11] Boilot JP, Salanié JP, Desplanches G, et al. (1979) Phase Transformation in Na1+xSixZr2P3–xO12 Compounds. Mater Res Bull 14: 1469–1477. doi: 10.1016/0025-5408(79)90091-6
    [12] Kohler H, Schultz H, Melnikov O (1983) Composition and Conduction Mechanism of the NASICON Structure-X-Ray Diffraction Study on two Crystals at Different Temperatures. Mater Res Bull 18: 1143–1152. doi: 10.1016/0025-5408(83)90158-7
    [13] Tsai CL, Hong HYP (1983) Investigation of phases and stability of solid electrolytes in the NASICON system. Mater Res Bull 18: 1399–1407. doi: 10.1016/0025-5408(83)90048-X
    [14] Clearfield A, Subramanian MA, Wang W, et al. (1983) The Use of Hydrothermal Procedures to Synthesize NASICON and Some Comments on the Stoichiometry of NASICON Phases. Solid State Ionics 9–10: 895–902.
    [15] Kohler H, Schultz H (1985) NASICON Solid Electrolytes Part I: The Na+-Diffusion Path and Its Relation to the Structure. Mater Res Bull 20: 1461–1471. doi: 10.1016/0025-5408(85)90164-3
    [16] Boilot JP, Collin G, Comes R (1983) Zirconium Deficiency in NASICON-Type Compounds: Crystal Structure of Na5Zr(PO4)3. J Solid State Chem 50: 91–99. doi: 10.1016/0022-4596(83)90236-0
    [17] Boilot JP, Collin G, Comes R (1983) Stoichiometry and phase transitions in NASICON type compounds. Solid State Ionics 9–10: 829–834.
    [18] Boilot JP, Collin G, Colomban Ph (1987) Crystal Structure of the True NASICON: Na3Zr2Si2PO12. Mater Res Bull 22: 669–676. doi: 10.1016/0025-5408(87)90116-4
    [19] Boilot JP, Colomban Ph, Collin G (1988) Stoichiometry-Structure-Fast Ion Conduction in the NASICON Solid Solution. Solid State Ionics 28–30: 403–410.
    [20] Lucco-Borlera M, Mazza D, Montanaro L, et al. (1997) X-ray characterization of the new NASICON compositions Na3Zr2−x/4Si2−xP1+xO12 with x = 0.333, 0.667, 1.000, 1.333, 1.667. Powder Diffr 12: 171–174.
    [21] Bohnke O, Ronchetti S, Mazza D (1999) Conductivity measurements on NASICON and nasicon-modified materials. Solid State Ionics 122: 127–136. doi: 10.1016/S0167-2738(99)00062-4
    [22] Naqash S, Ma Q, Tietz F, et al. (2017) Na3Zr2(SiO4)2(PO4) prepared by a solution-assisted solid state reaction. Solid State Ionics 302: 83–91. doi: 10.1016/j.ssi.2016.11.004
    [23] Engell J, Mortensen S, Møller L (1983) Fabrication of NASICON Electrolytes from Metal Alkoxide Derived Gels. Solid State Ionics 9–10: 877–884.
    [24] Warhus U (1986) Synthese und Stabilität des NASICON Mischkristallsystems (Na1+xZr2SixP3−xO12, 0 ≤ x ≤ 3) [PhD thesis]. University of Stuttgart.
    [25] Kreuer KD, Kohler H, Maier J (1989) Sodium Ion Conductors with NASICON Framework Structure, In: Takahashi T, High Conductivity Ionic Conductors: Recent Trends and Application, Singapore: World Scientific Publishing Co., 242–279.
    [26] Warhus U, Maier J, Rabenau A (1988) Thermodynamics of NASICON (Na1+xZr2SixP3−xO12). J Solid State Chem 72: 113–125. doi: 10.1016/0022-4596(88)90014-X
    [27] Mason TO, Hummel FA (1974) Compatibility Relations in the System SiO2-ZrO2-P2O5. J Am Ceram Soc 57: 538–539. doi: 10.1111/j.1151-2916.1974.tb10808.x
    [28] Turkdogan ET, Maddocks WR (1952) Phase Equilibrium Investigation of the Na2O-SiO2-P2O5 Ternary System. J Iron Steel Inst 172: 1–15.
    [29] Milne SJ, West AR (1983) Compound formation and conductivity in the system Na2O-ZrO2-P2O5: Sodium zirconium orthophosphates. Solid State Ionics 9–10: 865–868.
    [30] Milne SJ, West AR (1985) Zr-Doped Na3PO4: Crystal Chemistry, Phase Relations, and Polymorphism. J Solid State Chem 57: 166–177. doi: 10.1016/S0022-4596(85)80006-2
    [31] Vlna M, Petrosyan Y, Kovar V, et al. (1993) Phase Coexistence in the System Na2O-P2O5-ZrO2. Chem Pap 47: 296–297.
    [32] D'Ans J, Löffler J (1930) Untersuchungen im System Na2O-SiO2-ZrO2. Z Anorg Allg Chem 191: 1–35. doi: 10.1002/zaac.19301910102
    [33] Polezhaev YM, Chukhlantsev VG (1965) Triangulation of the System Na2O-ZrO2-SiO2. Izv Akad Nauk SSSR Neorg Mater 1: 1990–1993; Inorg Mater (Engl Transl) 1: 1797–1800.
    [34] Sircar A, Brett NH (1970) Phase Equilibria in Ternary Systems Containing Zirconia and Silica, IV. Preliminary Study of the System Na2O-ZrO2-SiO2. Trans Brit Ceram Soc 69: 131–135.
    [35] Wilson G, Glasser FP (1987) Subsolidus Phase Relations in the System Na2O-ZrO2-SiO2. Brit Ceram Trans J 86: 199–201.
    [36] Nicholas VA, Heyns AM, Kingon AI, et al. (1986) Reactions in the formation of Na3Zr2Si2PO12. J Mater Sci 21: 1967–1973. doi: 10.1007/BF00547935
    [37] Rudolf PR, Subramanian MA, Clearfield A, et al. (1985) The Crystal Structure of a Nonstoichiometric NASICON. Mater Res Bull 20: 643–651. doi: 10.1016/0025-5408(85)90142-4
    [38] Rudolf PR, Clearfield A, Jorgensen JD (1986) Rietveld Refinement Results on Three Nonstoichiometric Monoclinic NASICONs. Solid State Ionics 21: 213–224. doi: 10.1016/0167-2738(86)90075-5
    [39] Yde-Andersen S, Lundgaard JS, Møller L, et al. (1984) Properties of NASICON Electrolytes Prepared from Alkoxide Derived Gels: Ionic Conductivity, Durability in Molten Sodium and Strength Test Data. Solid State Ionics 14: 73–79. doi: 10.1016/0167-2738(84)90014-6
    [40] Perthuis H, Colomban Ph (1986) Sol-Gel Routes Leading to Nasicon Ceramics. Ceram Int 12: 39–52. doi: 10.1016/S0272-8842(86)80008-6
    [41] Maier J, Warhus U, Gmelin E (1986) Thermodynamic and Electrochemical Investigations of the NASICON Solid Solution System. Solid State Ionics 18–19: 969–973.
    [42] Boilot JP, Collin G, Colomban Ph (1988) Relation Structure-Fast Ion Conduction in the NASICON Solid Solution. J Solid State Chem 73: 160–171. doi: 10.1016/0022-4596(88)90065-5
    [43] Colomban Ph (1986) Orientational Disorder, Glass/Crystal Transition and Superionic Conductivity in NASICON. Solid State Ionics 21: 97–115. doi: 10.1016/0167-2738(86)90201-8
    [44] Park H, Jung K, Nezafati M, et al. (2016) Sodium Ion Diffusion in Nasicon (Na3Zr2Si2PO12) Solid Electrolytes: Effects of Excess Sodium. ACS Appl Mater Interfaces 8: 27814–27824. doi: 10.1021/acsami.6b09992
    [45] Kafalas JA, Cava JR (1979) Effect of Pressure and Composition of Fast Na+-Ion Transport in the System Na1+xZr2SixP3−xO12. Proceedings of the International Conference on Fast Ion Transport in Solids, 419–422.
    [46] Kreuer KD, Warhus U (1986) NASICON Solid Electrolytes: Part IV Chemical Durability. Mater Res Bull 21: 357–363. doi: 10.1016/0025-5408(86)90193-5
  • Reader Comments
  • © 2017 the Author(s), licensee AIMS Press. This is an open access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0)
通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

Metrics

Article views(5889) PDF downloads(1787) Cited by(12)

Article outline

Figures and Tables

Figures(7)  /  Tables(1)

Other Articles By Authors

/

DownLoad:  Full-Size Img  PowerPoint
Return
Return

Catalog