Structure and properties of NASICON synthesized by two different zirconium salts

Abstract

ZrOCl₂·8H₂O and ZrO(NO₃)₂·2H₂O were used respectively to synthesize a NASICON solid electrolyte by a sol-gel method. The structure and properties of two samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). The crystal structure was investigated by the Rietveld refinement. It is found that both the samples contain a monoclinic C2/c phase as the main conductive phase with the lattice parameters of a=1.56312 nm, b=0.90784 nm and c=0.92203 nm, though a small amount of rhombohedral phase is also detected in the final product. The sample synthesized by ZrO(NO₃)₂·2H₂O contains more monoclinic phase (89.48wt%) than that synthesized by ZrOCl₂·8H₂O (74.91wt%). As expected, the ionic conductivity of the latter is higher than that of the former; however, the activation energy of the latter (0.37 eV) is slightly higher than that of the former (0.35 eV).

Keywords

NASICON / superionic conducting materials / sodium compounds / sol-gel process / microstructure / electrical conductivity

References

[1] Hong H.Y.P. Crystal structures and crystal chemistry in the system Na_1+xZr₂Si_xP_3−xO₁₂. Mater. Res. Bull., 1976, 11(2): 173

[2] Goodenough J.B., Hong H.Y.P., Kafalas J.A. Fast Na⁺-ion transport in skeleton structure. Mater. Res. Bull., 1976, 11(2): 203

[3] Zhu D., Luo F., Xie Z., Zhou W. Preparation and characteristic of NASICON ceramics. Rare Met., 2006, 25(6): 39

[4] Morio M., Hyodo T., Shimizu Y., Egashira M. Effect of macrostructural control of an auxiliary layer on the CO₂ sensing properties of NASICON-based gas sensors. Sens. Actuators B, 2009, 139(2): 563

[5] Kida T., Seo M.H., Kishi S., Kanmura Y., Yamazoe N., Shimanoe K. Application of a solid electrolyte CO₂ sensor for the analysis of standard volatile organic compound gases. Anal. Chem., 2010, 82(8): 3315

[6] Kida T., Kishi S., Yamazoe N., Shimanoe K. Stability and interfacial structure of a NASICON-based CO₂ sensor fitted with a solid-reference electrode. Sens. Lett., 2011, 9(1): 288

[7] Kida T., Morinaga N., Kishi S., An K.M., Sim K.W., Chae B.Y., Kim J.K., Ryu B.K., Shimanoe K. Electrochemical detection of volatile organic compounds using a Na₃Zr₂Si₂PO₁₂/Bi₂Cu_0.1V_0.9O_5.35 heterojunction device. Electrochim. Acta, 2011, 56(22): 7484

[8] Alpen U. v., Bell M.F., Wichelhaus W. Phase transition in NASICON (Na₃Zr₂Si₂PO₁₂). Mater. Res. Bull., 1979, 14(10): 1317

[9] Yoldas B.E., Lloyd I.K. Nasicon formation by chemical polymerization. Mater. Res. Bull., 1983, 18(10): 1171

[10] Yang Y., Liu C.C. Development of a NASICON-based amperometric carbon dioxide sensor. Sens. Actuators B, 2000, 62(1): 30

[11] He Y., Quan B., Wang B., Zhang C., Liu F. Investigation of miniature CO₂ gas sensor based on NASICON. Russ. J. Electrochem., 2007, 43(11): 1289

[12] Wang B., Liang X.S., Liu F.M., Zhong T.G., Zhao C., Lu G.Y., Quan B.F. Synthesis and characterization of NASICON nanoparticles by sol-gel method. Chem. Res. Chin. Univ., 2009, 25(1): 13.

[13] Liang X.S., Yang S.Q., Zhong T.G., Diao Q., Zhang H., Li J.G., Quan B.F., Lu G.Y. Mixed potential type carbon monoxide sensor utilizing NASICON and spinel type oxide electrode. Sens. Lett., 2011, 9(2): 832

[14] Zhang S., Quan B.F., Zhao Z.Y., Zhao B.G., He Y.H., Chen W.Y. Preparation and characterization of NASICON with a new sol-gel process. Mater. Lett., 2003, 58(1–2): 226.

[15] Dang H.Y., Guo X.M. Investigation of porous counter electrode for the CO₂ sensing properties of NASICON-based gas sensor. Solid State Ionics, 2011, 201(1): 68

[16] Baumann F.S., Fleig J., Habermeier H.U., Maier J. Impedance spectroscopic study on well-defined (La,Sr)-(Co,Fe)O_3−δ model electrodes. Solid State Ionics, 2006, 177(11–12): 1071

[17] Aono H., Imanaka N., Adachi G.Y. High Li⁺ conducting ceramics. Acc. Chem. Res., 1994, 27(9): 265

[18] Lee J.S., Chang C.M., Lee Y.I., Lee J.H., Hong S.H. Spark plasma sintering (SPS) of NASICON ceramics. J. Am. Ceram. Soc., 2004, 87(2): 305

[19] Dang H.Y., Guo X.M. Characteristics of NASICON-based thick-film CO₂ sensor attached with integrated auxiliary electrode. IEEE Sens. J., 2012, 12(7): 2430

[20] Yde-Andersen S., Lundsgaard J.S., Møller L., Engell J. Properties of NASICON electrolytes prepared from alkoxide derived gels: ionic conductivity, durability in molten sodium and strength test data. Solid State Ionics, 1984, 14(1): 73

[21] Bogusz W., Krok F., Piszczatowski W. Particular features of admittance spectra of polycrystalline NASICON samples. Solid State Ionics, 1999, 119(1–4): 165

[22] Traversa E., Aono H., Sadaoka Y., Montanaro L. Electrical properties of sol-gel processed NASICON having new compositions. Sens. Actuators B, 2000, 65(1): 204

[23] Essoumhi A., Favotto C., Mansori M., Satre P. Synthesis and characterization of a NASICON series with general formula Na_2.8Zr_2−ySi_1.8−4yP_1.2+4yO₁₂ (0≤y≤0.45). J. Solid State Chem., 2004, 177(12): 4475