Lithium-Content-Dependent Ionic Conductivity of NASICON-Type LATP Solid Electrolytes Synthesized by the Molten Flux Method


Views: 1 / PDF downloads: 0

Authors

DOI:

https://doi.org/10.32523/3107-278X-2026-156-3-51-65

Keywords:

lithium-ion batteries, RF magnetron sputtering, annealing, electrochemical performance

Abstract

The article provides a comparative assessment of the structural and electrochemical properties of lithium aluminum titanium phosphate (LATP) solid electrolytes with different lithium contents  LATP (Li1.3-1.5AlxTi2-x(PO4)3). LATP polycrystals with NASICON-type structure were synthesized by the molten flux method, which included mixing LiNO3, Al2O3, TiO2, NH4H2PO4 and CO(NH2)2 precursors, followed by staged heating at 170°C, 500°C, and 800°C, pressing, and final sintering at 800°C for 4 hours. X-ray diffraction analysis confirmed the formation of the main LATP crystalline phase, while an increase in lithium concentration led to the appearance of secondary phases such as Li4P2O7, AlPO4, and TiP2O7, which affected ionic conductivity. Electrochemical impedance spectroscopy showed that LATP (Li1.4) exhibits the highest ionic conductivity (1.66-1.85 × 10-4 S/cm at 25°C) compared to Li1.3 and Li1.5 samples due to its higher structural density and optimal phase composition. The temperature dependence analysis revealed that increasing temperature enhances lithium-ion mobility, confirming thermally activated ion transport. Therefore, the Li1.4Al0.4Ti1.6(PO4)3 composition demonstrates the most promising characteristics as a solid electrolyte for all-solid-state lithium batteries.

Downloads

Download data is not yet available.

References

Waetzig, K., Rost, A., Heubner, C., Coeler, M., Nikolowski, K., Wolter, M., & Schilm, J. (2020). Synthesis and sintering of Li1.3Al0.3Ti1.7(PO4)3 (LATP) electrolyte for ceramics with improved Li+ conductivity. Journal of Alloys and Compounds, 818, 153237. https://doi.org/10.1016/j.jallcom.2019.153237

Zhang, B., Tan, R., Yang, L., Zheng, J., Zhang, K., Mo, S., & Pan, F. (2018). Mechanisms and properties of ion-transport in inorganic solid electrolytes. Energy Storage Materials, 10, 139–159. https://doi.org/10.1016/j.ensm.2017.10.015

Liu, Y., Sun, Q., Zhao, Y., Wang, B., Kaghazchi, P., Adair, K. R., & Sun, X. (2018). Stabilizing the interface of NASICON solid electrolyte against Li metal with atomic layer deposition. ACS Applied Materials & Interfaces, 10(37), 31240–31248. https://doi.org/10.1021/acsami.8b10924

Yang, Z., Yuan, H., Zhou, C., Wu, Y., Tang, W., Sang, S., & Liu, H. (2020). Facile interfacial adhesion enabled LATP-based solid-state lithium metal battery. Chemical Engineering Journal, 392, 123650. https://doi.org/10.1016/j.cej.2019.123650

Zhu, X. B., Zhao, T. S., Wei, Z. H., Tan, P., & Zhao, G. (2015). A novel solid-state Li–O2 battery with an integrated electrolyte and cathode structure. Energy & Environmental Science, 8(9), 2782–2790. https://doi.org/10.1039/C5EE01353G

Zhang, X., Butenko, D., Gao, L., Ye, X., Hong, B., Han, S., & Zhu, J. (2023). Synergistic ion diffusion in lithium titanium phosphate conductors: a tale from solo to ensemble. Chemistry of Materials, 35(11), 4541–4548. https://doi.org/10.1021/acs.chemmater.3c00479

Moustafa, M. G., Sanad, M. M. S., & Hassaan, M. Y. (2020). NASICON-type lithium iron germanium phosphate glass ceramic nanocomposites as anode materials for lithium ion batteries. Journal of Alloys and Compounds, 845, 156338. https://doi.org/10.1016/j.jallcom.2020.156338

Wolfenstine, J., Allen, J. L., Sakamoto, J., Siegel, D. J., & Choe, H. (2018). Mechanical behavior of Li-ion-conducting crystalline oxide-based solid electrolytes: a brief review. Ionics, 24(5), 1271–1276. https://doi.org/10.1007/s11581-017-2374-2

Bachman, J. C., Muy, S., Grimaud, A., Chang, H. H., Pour, N., Lux, S. F., Paschos, O., Maglia, F., Lupart, S., Lamp, P., & Shao-Horn, Y. (2016). Inorganic solid-state electrolytes for lithium batteries: Mechanisms and properties governing ion conduction. Chemical Reviews, 116(1), 140–162. https://doi.org/10.1021/acs.chemrev.5b00563

Randau, S., Weber, D. A., Kötz, O., Koerver, R., Braun, P., Weber, A., Ivers-Tiffée, E., & Janek, J. (2020). Benchmarking the performance of all-solid-state lithium batteries. Nature Energy, 5(3), 259–270. https://doi.org/10.1038/s41560-020-0565-1

Reddy, M. V., Julien, C. M., Mauger, A., Zaghib, K., & Chowdari, B. V. R. (2020). Sulfide and oxide inorganic solid electrolytes for all-solid-state Li batteries: A review. Nanomaterials, 10(8), 1606. https://doi.org/10.3390/nano10081606

Zhang, Z., Shao, Y., Lotsch, B., Hu, Y. S., Li, H., Janek, J., Nazar, L. F., Nan, C. W., Maier, J., Armand, M., & Chen, L. (2018). New horizons for inorganic solid state ion conductors. Energy & Environmental Science, 11(8), 1945–1976. https://doi.org/10.1039/C8EE01053F

Wu, P., Zhou, W., Su, X., Li, J., Su, M., Zhou, X., & Lu, W. (2023). Recent advances in conduction mechanisms, synthesis methods, and improvement strategies for Li1+xAlxTi2−x(PO4)3 solid electrolyte for all‐solid‐state lithium batteries. Advanced Energy Materials, 13(4), 2203440. https://doi.org/10.1002/aenm.202203440

Xiao, W., Wang, J., Fan, L., Zhang, J., & Li, X. (2019). Recent advances in Li1+xAlxTi2−x(PO4)3 solid-state electrolyte for safe lithium batteries. Energy Storage Materials, 19, 379–400. https://doi.org/10.1016/j.ensm.2018.10.008

Lovett, A. J., Kursumovic, A., & MacManus-Driscoll, J. L. (2024). Lithium loss in vacuum deposited thin films. ACS Energy Letters, 9(4), 1753–1758. https://doi.org/10.1021/acsenergylett.4c00315

Nuernberg, R. B., Landry, A. K., Le Cras, F., & Le Cras, B. P. (2024). Enhancing ionic conductivity of LiSiPON thin films electrolytes: Overcoming synthesis challenges related to Li-migration in the precursor target. Solid State Ionics, 418, 116723. https://doi.org/10.1016/j.ssi.2024.116723

Tolganbek, N., Yerkinbekova, Y., Khairullin, A., Bakenov, Z., Kanamura, K., & Mentbayeva, A. (2021). Enhancing purity and ionic conductivity of NASICON-typed Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte. Ceramics International, 47(13), 18188–18195. https://doi.org/10.1016/j.ceramint.2021.03.104

Mashekova, A., Baltash, Y., Yegamkulov, M., Trussov, I., Bakenov, Z., & Mukanova, A. (2022). Polycationic doping of the LATP ceramic electrolyte for Li-ion batteries. RSC Advances, 12(46), 29595–29601. https://doi.org/10.1039/D2RA04924A

Baltash, Y., Mashekova, A., Yegamkulov, M., Trussov, I., Bakenov, Z., & Mukanova, A. (2023). Silicon doping of LATP via molten flux method. Ionics, 29(7), 2647–2655. https://doi.org/10.1007/s11581-023-05032-4

DeWees, R., & Wang, H. (2019). Synthesis and properties of NaSICON-type LATP and LAGP solid electrolytes. ChemSusChem, 12(16), 3713–3725. https://doi.org/10.1002/cssc.201900725

Arbi, K., Rojo, J. M., & Sanz, J. (2007). Lithium mobility in titanium based Nasicon Li1+xTi2−xAlx(PO4)3 and LiTi2−xZrx(PO4)3 materials followed by NMR and impedance spectroscopy. Journal of the European Ceramic Society, 27(13–15), 4215–4218. https://doi.org/10.1016/j.jeurceramsoc.2007.02.092

Liu, J., Liu, T., Pu, Y., Guan, M., Tang, Z., Ding, F., & Li, Y. (2017). Facile synthesis of NASICON-type Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte and its application for enhanced cyclic performance in lithium ion batteries through the introduction of an artificial Li3PO4 SEI layer. RSC Advances, 7(74), 46545–46552. https://doi.org/10.1039/C7RA08659A

Ma, Q., Xu, Q., Tsai, C. L., Tietz, F., & Guillon, O. (2016). A Novel Sol-Gel Method for Large‐Scale Production of Nanopowders: Preparation of Li1.5Al0.5Ti1.5(PO4)3 as an Example. Journal of the American Ceramic Society, 99(2), 410–414. https://doi.org/10.1111/jace.13930

Yang, K., Chen, L., Ma, J., He, Y. B., & Kang, F. (2021). Progress and perspective of Li1+xAlxTi2−x(PO4)3 ceramic electrolyte in lithium batteries. InfoMat, 3(11), 1195–1217. https://doi.org/10.1002/inf2.122

Öksüzoğlu, F., Ateş, Ş., Özkendir, O. M., Çelik, G., Eker, Y. R., & Baveghar, H. (2024). Structure and ionic conductivity of NASICON-type LATP solid electrolyte synthesized by the solid-state method. Ceramics International, 50(17), 31435–31441. https://doi.org/10.1016/j.ceramint.2024.05.214

Xiao, W., Li, J., Miao, C., Xin, Y., Nie, S., Liu, C., & He, M. (2023). Engineering and regulating the interfacial stability between Li1.3Al0.3Ti1.7(PO4)3-based solid electrolytes and lithium metal anodes for solid-state lithium batteries. Journal of Colloid and Interface Science, 652, 1447–1455. https://doi.org/10.1016/j.jcis.2023.08.083

Downloads

Published

2026-10-01

Issue

Section

Chemistry

Similar Articles

<< < 1 2 3 4 

You may also start an advanced similarity search for this article.