Lithium ion conductivity, crystallization tendency, and microstructural evolution of LiZrxTi2-x(PO4)3 NASICON glass-ceramics (x = 0 - 0.4)

  • Parisa Goharian 1
  • Alireza Aghaei 1
  • Bijan Eftekhari Yekta 2
  • Sara Banijamali 1
  • 1 Ceramic Department, Materials and Energy Research Center (MERC), Alborz, Iran
  • 2 School of Metallurgy & Materials Engineering, Iran University of Science and Technology, Tehran, Iran


In this research, NASICON type (LiZrxTi2-x(PO4)3) glass-ceramics were fabricated (x = 0.1, 0.2, 0.3, and 0.4). Lithium-ion conductivity along with the crystallization tendency and microstructural features were examined in this regard. Parent glasses obtained through melt quenching were converted to the glass-ceramic specimens after one-step heat treatment procedure. The resultant glass-ceramics were deeply explored by means of different techniques including scanning electron microscope, differential thermal analysis, X-ray diffractometry, and ionic conductivity measurements. According to the obtained results, presence of Zr4+ ions in the glass network and its gradual increase caused the enhanced crystallization temperature as well as declined crystallinity and microstructure coarsening. In all studied glass-ceramics, LiT2(PO4)3 solid solution was the dominant crystalline phase and Zr4+ ions partly substituted in the structure of this crystalline phase. Moreover, presence of Zr4+ ions in the glass composition resulted in diminished lithium-ion conductivity of corresponded glass-ceramics at ambient temperature. Consequently, total conductivity of specimen with the highest level of ZrO2 (x = 0.4) was measured to be 0.78 x 10-5 Scm-1, being considerably less than ionic conductivity of the base (x = 0) glass-ceramic (3.04 x 10-5 Scm-1). It seems that less crystallinity of ZrO2 containing glass-ceramics decreases required connectivity between the lithium-ion free paths and is responsible for the diminished ionic conductivity of these specimens.


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Keywords: Glass-ceramic, Crystallization, Ionic conductivity, Zirconium ions, NASICON


[1] Y. Yang, R. Wang, Z. Shen, Q. Yu, R. Xiong, W. Shen, Towards a safer lithium ion batteries: A critical review on cause, characteristics, warning and disposal strategy for thermal runaway, Adv. Appl. Energy. 11 (2023) 100146.
[2] F. Maisel, C. Neef, F. Marscheider-Weidemann, N.F. Nissen, A forecast on future raw material demand and recycling potential of lithium-ion batteries in electric vehicles, Resour. Conserv. Recy. 192 (2023) 106920.
[3] S.V. Gaslov, M.S. Rublev, A.E. Biryukov, S.O. Kopytov, Virtual simulation of the operation of a lithium-ion battery as a part of a vehicle using ID complex model, Transport. Res. Procedia. 68 (2023) 906–916.
[4] Z. Kou, C. Miao, Z. Wang, W. Xiao, Novel NASICON-type structural Li1.3Al0.3Ti1.7SixP5(3-0.8x)O12 solid electrolytes with improved ionic conductivity for lithium ion batteries, Solid State Ion. 343 (2019) 115090.
[5] H. Gan, W. Zhu, L. Zhang, Y. Jia, Zr doped NASICON-type LATP glass-ceramic as a super-thin coating onto deoxidized carbon wrapped CNT-S cathode for lithium-sulphur battery, Electrochim. Acta. 423 (2022) 140567.
[6] S. Jia, H. Akamatsu, G. Hasegawa, S. Ohno, K. Hayashi, Glass-ceramic route to NASICON-type NaxTi2(PO4)3 electrodes for Na-ion batteries, Ceram. Int. 48 (2022) 24758–24764.
[7] M.G. Moustafa, M.M. S. Sanad, M.Y. Hassaan, NASICON-type lithium iron germanium phosphate glass-ceramic nanocomposites as anode materials for lithium ion batteries, J. Alloys Compd. 845 (2020) 156338.
[8] Y. Shao, G. Zhong, Y. Lu, L. Liu, C. Zhao, et al., A novel NASICON-based glass-ceramic composite electrolyte with enhanced Na-ion conductivity, Energy Storage Mater. 23 (2019) 514–521.
[9] J.M. Valle, C. Huang, D. Tatke, J. Wolfenstine, Characterization of hot-pressed von Alpen type NASICON ceramic electrolytes, Solid State Ion. 369 (2021) 115712.
[10] S. Saffirio, M. Falco, G.B. Appectecchi, F. Smeacetto, C. Gerbaldi, Li1.4Al0.4Ge0.4Ti1.4(PO4)3 promising NASICON-structured glass-ceramic electrolyte for all solid state Li-based batteries: Unravelling the effect of diboron trioxide, J. Eur. Ceram. Soc. 42 (2022) 1023–1032.
[11] J.M. Naranjo-Balseca, C.S. Martinez-Cisneros, B. Pandit, A. Varez, High performance NASICON ceramic electrolytes produced by tape-casting and low temperature hot-pressing: Towards sustainable all-solid-state sodium batteries operating at room temperature, J. Eur. Ceram. Soc. 43 (2023) 4826–4836.
[12] R.P. Rao, C. Maohua, S. Adams, Preparation and characterization of Nasicon type Li ionic conductor, J. Solid State Electrochem. 16 (2012) 3349–3354.
[13] P.Goharian, A. Aghaei, B. Eftekhari, S. Banijamali, Ionic conductivity and microstructural evaluatuion of Li2O-TiO2-P2O5-SiO2 glass-ceramics, Ceram. Int. 41 (2015) 1757–1763.
[14] B. Zarabian, B. Eftekhari Yekta, S. Banijamali, Crystallization behavior and ionjic conductivity of NASICON type glass-ceramics containing different amounts of B2O3, Synth. Sinter. 3 (2023) 1419.
[15] P.Goharian, B. Eftekhari, A. Aghaei, S. Banijamali, Lithium-ion conducting glass-ceramics in the system Li2O-TiO2-P2O5-Cr2O3-SiO2, J. Non-Cryst. Solids. 409 (2015) 120–125.
[16] A. Chandra, A. Bhatt, A. Chandra, Ion conduction in superionic glassy electrolytes: An overview, J. Mater. Sci. Tech. 29 (2013) 193–208.

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Lithium ion conductivity, crystallization tendency, and microstructural evolution of LiZrxTi2-x(PO4)3 NASICON glass-ceramics (x = 0 - 0.4)
How to Cite
Goharian, P., Aghaei, A., Eftekhari Yekta, B., & Banijamali, S. (2023). Lithium ion conductivity, crystallization tendency, and microstructural evolution of LiZrxTi2-x(PO4)3 NASICON glass-ceramics (x = 0 - 0.4). Synthesis and Sintering, 3(2), 67-72.

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