Novel Sn-Doped NASICON-Type Na_3.2Zr₂Si_2.2P_0.8O₁₂ Solid Electrolyte With Improved Ionic Conductivity for a Solid-State Sodium Battery

Abstract

Solid electrolytes face challenges in solid-state sodium batteries (SSSBs) because of limited ionic conductivity, increased interfacial resistance, and sodium dendrite issues. In this study, we adopted a unique Sn⁴⁺ doping strategy for Na_3.2Zr₂Si_2.2P_0.8O₁₂ (NZSP) that caused a partial structural transition from the monoclinic (C2/c) phase to the rhombohedral (R-3c) phase in Na_3.2Zr_1.9Sn_0.1Si_2.2P_0.8O₁₂ (NZSnSP1). X-ray diffraction (XRD) patterns and high-resolution transmission electron microscopy analyses were used to confirm this transition, where rhombohedral NZSnSP1 showed an increase in the Na2–O bond length compared with monoclinic NZSnSP1, increasing its triangular bottleneck areas and noticeably enhancing Na⁺ ionic conductivity, a higher Na transference number, and lower electronic conductivity. NZSnSP1 also showed exceptionally high compatibility with Na metal with an increased critical current density, as evidenced by symmetric cell tests. The SSSB, fabricated using Na_0.9Zn_0.22Fe_0.3Mn_0.48O₂ (NZFMO), Na metal, and NZSnSP1 as the cathode, anode, and the solid electrolyte and separator, respectively, maintains 65.86% of retention in the reversible capacity over 300 cycles within a voltage range of 2.0–4.0 V at 25°C at 0.1 C. The in-situ X-ray diffraction and X-ray absorption analyses of the P and Zr K-edges confirmed that NZSnSP1 remained highly stable before and after electrochemical cycling. This crystal structure modification strategy enables the synthesis of ideal solid electrolytes for practical SSSBs.

Keywords

ionic conductivity / NASICON-type solid electrolyte / phase transition / Sn doping / solid-state battery

References

[1] P. Lu, F. Ding, Z. Xu, J. Liu, X. Liu, and Q. Xu, “Study on (100-x)(70Li₂S-30P₂S₅)-xli₂ZrO₃ Glass- Ceramic Electrolyte for All-Solid-State Lithium-Ion Batteries,” Journal of Power Sources 356 (2017): 163-171.

[2] Y. Meesala, Y. K. Liao, A. Jena, et al., “An Efficient Multi-Doping Strategy to Enhance Li-Ion Conductivity in the Garnet-Type Solid Electrolyte Li₇La₃Zr₂O₁₂,” Journal of Materials Chemistry A 7, no. 14 (2019): 8589-8601.

[3] C. Wen, Z. Luo, H. Liang, X. Liu, W. Lei, and A. Lu, “Effect of Sintering Temperature and Holding Time on the Crystal Phase, Microstructure, and Ionic Conductivity of NASICON-Type 33Na₂O-40ZrO₂-40SiO₂-10P₂O₅ Solid Electrolytes,” Applied Physics A 128 (2022): 71.

[4] H. Duan, H. Zheng, Y. Zhou, B. Xu, and H. Liu, “Stability of Garnet-Type Li Ion Conductors: An Overview,” Solid State Ionics 318 (2018): 45-53.

[5] Y. Ren, K. Chen, R. Chen, T. Liu, Y. Zhang, and C. W. Nan, “Oxide Electrolytes for Lithium Batteries,” Journal of the American Ceramic Society 98, no. 12 (2015): 3603-3623.

[6] C. Sun, J. Liu, Y. Gong, D. P. Wilkinson, and J. Zhang, “Recent Advances in All-Solid-State Rechargeable Lithium Batteries,” Nano Energy 33 (2017): 363-386.

[7] Z. Wu, Z. Xie, A. Yoshida, et al., “Utmost Limits of Various Solid Electrolytes in All-Solid-State Lithium Batteries: A Critical Review,” Renewable and Sustainable Energy Reviews 109 (2019): 367-385.

[8] J. B. Goodenough, H. Y. P. Hong, and J. A. Kafalas, “Fast Na⁺-Ion Transport in Skeleton Structures,” Materials Research Bulletin 11, no. 2 (1976): 203-220.

[9] S. T. Lee, D. H. Lee, S. M. Lee, S. S. Han, S. H. Lee, and S. K. Lim, “Effects of Calcium Impurity on Phase Relationship, Ionic Conductivity and Microstructure of Na⁺-β/β″-Alumina Solid Electrolyte,” Bulletin of Materials Science 39 (2016): 729-735.

[10] L. Zhang, K. Yang, J. Mi, et al., “Na₃PSe₄: A Novel Chalcogenide Solid Electrolyte With High Ionic Conductivity,” Advanced Energy Materials 5, no. 24 (2015): 1501294.

[11] Z. Zhang, Q. Zhang, C. Ren, et al., “A Ceramic/Polymer Composite Solid Electrolyte for Sodium Batteries,” Journal of Materials Chemistry A 4, no. 41 (2016): 15823-15828.

[12] F. Han, A. S. Westover, J. Yue, et al., “High Electronic Conductivity as the Origin of Lithium Dendrite Formation Within Solid Electrolytes,” Nature Energy 4, no. 3 (2019): 187-196.

[13] X. Shen, Q. Zhang, T. Ning, et al., “Effects of a Dual Doping Strategy on the Structure and Ionic Conductivity of Garnet-Type Electrolyte,” Solid State Ionics 356 (2020): 115427.

[14] S. Vasudevan, S. Dwivedi, and P. Balaya, “Overview and Perspectives of Solid Electrolytes for Sodium Batteries,” International Journal of Applied Ceramic Technology 20, no. 2 (2023): 563-584.

[15] S. He, Y. Xu, Y. Chen, and X. Ma, “Enhanced Ionic Conductivity of an F—Assisted Na₃Zr₂Si₂PO₁₂ Solid Electrolyte for Solid-State Sodium Batteries,” Journal of Materials Chemistry A 8, no. 25 (2020): 12594-12602.

[16] Y. Lu, J. A. Alonso, Q. Yi, L. Lu, Z. L. Wang, and C. Sun, “A High-Performance Monolithic Solid-State Sodium Battery With Ca²⁺ Doped Na₃Zr₂Si₂PO₁₂ Electrolyte,” Advanced Energy Materials 9, no. 28 (2019): 1901205.

[17] Q. Ma, M. Guin, S. Naqash, C. L. Tsai, F. Tietz, and O. Guillon, “Scandium-Substituted Na₃Zr₂(SiO₄)₂(PO₄) Prepared by a Solution-Assisted Solid-State Reaction Method as Sodium-Ion Conductors,” Chemistry of Materials 28, no. 13 (2016): 4821-4828.

[18] L. Wang and R. V. Kumar, “A New SO₂ Gas Sensor Based on an Mg²⁺ Conducting Solid Electrolyte,” Journal of Electroanalytical Chemistry 543, no. 2 (2003): 109-114.

[19] W. Wang, Z. Zhang, X. O.u., and J. Zhao, “Properties and Phase Relationship of the Na_1+xHf_2−yTi_ySi_xP_3−xO₁₂ System,” Solid State Ionics 28-30 (1988): 442-445.

[20] A. Xu, R. Wang, M. Yao, et al., “Electrochemical Properties of an Sn-Doped LATP Ceramic Electrolyte and Its Derived Sandwich-Structured Composite Solid Electrolyte,” Nanomaterials. 12, no. 12 (2022): 2082.

[21] C. Tantardini and A. R. Oganov, “Thermochemical Electronegativities of the Elements,” Nature Communications 12, no. 1 (2021): 2087.

[22] K. Singh, A. Chakraborty, R. Thirupathi, and S. Omar, “Recent Advances in NASICON-Type Oxide Electrolytes for Solid-State Sodium-Ion Rechargeable Batteries,” Ionics 28, no. 12 (2022): 5289-5319.

[23] Z. Zhang, Y. Shao, B. Lotsch, et al., “New Horizons for Inorganic Solid State Ion Conductors,” Energy & Environmental Science 11, no. 8 (2018): 1945-1976.

[24] J. Yang, G. Liu, M. Avdeev, et al., “Ultrastable All-Solid-State Sodium Rechargeable Batteries,” ACS Energy Letters 5, no. 9 (2020): 2835-2841.

[25] S. Mehraz, P. Kongsong, A. Taleb, N. Dokhane, and L. Sikong, “Large Scale and Facile Synthesis of Sn Doped TiO₂ Aggregates Using Hydrothermal Synthesis,” Solar Energy Materials and Solar Cells 189 (2019): 254-262.

[26] G. D. Park, J. K. Lee, and Y. Chan Kang, “Design and Synthesis of Janus-Structured Mutually Doped SnO₂-Co₃O₄ Hollow Nanostructures as Superior Anode Materials for Lithium-Ion Batteries,” Journal of Materials Chemistry A 5, no. 48 (2017): 25319-25327.

[27] B. Roose, J. P. C. Baena, K. C. Gödel, et al., “Mesoporous SnO₂ Electron Selective Contact Enables UV-Stable Perovskite Solar Cells,” Nano Energy 30 (2016): 517-522.

[28] A. Venkateswara Rao, V. Veeraiah, A. V. Prasada Rao, B. Kishore Babu, and M. Brahmayya, “Spectroscopic Characterization and Conductivity of Sn-Substituted Liti₂(PO₄)₃,” Research on Chemical Intermediates 41 (2015): 4327-4337.

[29] K. Wang, G. Teng, J. Yang, et al., “Sn (II,IV) Steric and Electronic Structure Effects Enable Self-Selective Doping on Fe/Si-Sites of Li₂FeSiO₄ Nanocrystals for High Performance Lithium Ion Batteries,” Journal of Materials Chemistry A 3 (2015): 24437-24445.

[30] Y. Shao, G. Zhong, Y. Lu, et al., “A Novel NASICON-Based Glass-Ceramic Composite Electrolyte With Enhanced Na-Ion Conductivity,” Energy Storage Materials 23 (2019): 514-521.

[31] C. Zhao, L. Liu, X. Qi, et al., “Solid-State Sodium Batteries,” Advanced Energy Materials 8, no. 17 (2018): 1703012.

[32] S. Liu, C. Zhou, Y. Wang, et al., “Ce-Substituted Nanograin Na₃Zr₂Si₂PO₁₂ Prepared by LF- FSP as Sodium-Ion Conductors,” ACS Applied Materials & Interfaces 12, no. 3 (2019): 3502-3509.

[33] Q. Wang, C. Yu, L. Li, et al., “Sc-Doping in Na₃Zr₂Si₂PO₁₂ Electrolytes Enables Preeminent Performance of Solid-State Sodium Batteries in a Wide Temperature Range,” Energy Storage Materials 54 (2023): 135-145.

[34] Y. Ruan, F. Guo, J. Liu, S. Song, N. Jiang, and B. Cheng, “Optimization of Na₃Zr₂Si₂PO₁₂ Ceramic Electrolyte and Interface for High Performance Solid-State Sodium Battery,” Ceramics International 45, no. 2 (2019): 1770-1776.

[35] J. A. S. Oh, L. He, A. Plewa, et al., “Composite NASICON (Na₃Zr₂Si₂PO₁₂) Solid-State Electrolyte With Enhanced Na⁺ Ionic Conductivity: Effect of Liquid Phase Sintering,” ACS Applied Materials & Interfaces 11, no. 43 (2019): 40125-40133.

[36] J. Yang, H. L. Wan, Z. H. Zhang, et al., “NASICON-Structured Na_3.1Zr_1.95Mg_0.05Si₂PO₁₂ Solid Electrolyte for Solid-State Sodium Batteries,” Rare Metals 37 (2018): 480-487.

[37] S. Naqash, Q. Ma, F. Tietz, and O. Guillon, “Na₃Zr₂(SiO₄)₂(PO₄) Prepared by a Solution-Assisted Solid State Reaction,” Solid State Ionics 302 (2017): 83-91.

[38] Y. Wang, S. Song, C. Xu, N. Hu, J. Molenda, and L. Lu, “Development of Solid-State Electrolytes for Sodium-Ion Battery—A Short Review,” Nano Materials Science 1, no. 2 (2019): 91-100.

[39] G. Assat, S. L. Glazier, C. Delacourt, and J. M. Tarascon, “Probing the Thermal Effects of Voltage Hysteresis in Anionic Redox-Based Lithium-Rich Cathodes Using Isothermal Calorimetry,” Nature Energy 4, no. 8 (2019): 647-656.

[40] V. J. Ovejas and A. Cuadras, “Effects of Cycling on Lithium-Ion Battery Hysteresis and Overvoltage,” Scientific Reports 9, no. 1 (2019): 14875.

[41] Y. Ren, Y. Shen, Y. Lin, and C. W. Nan, “Direct Observation of Lithium Dendrites Inside Garnet-Type Lithium-Ion Solid Electrolyte,” Electrochemistry Communications 57 (2015): 27-30.

[42] L. Cheng, E. J. Crumlin, W. Chen, et al., “The Origin of High Electrolyte-Electrode Interfacial Resistances in Lithium Cells Containing Garnet Type Solid Electrolytes,” Physical Chemistry Chemical Physics 16, no. 34 (2014): 18294-18300.

[43] X. Li, D. Wu, Y. N. Zhou, L. Liu, X. Q. Yang, and G. Ceder, “O3-type Na(Mn_0.25Fe_0.25Co_0.25Ni_0.25)O₂: A Quaternary Layered Cathode Compound for Rechargeable Na Ion Batteries,” Electrochemistry Communications 49 (2014): 51-54.

[44] L. Mu, S. Xu, Y. Li, et al., “Prototype Sodium-Ion Batteries Using an Air-Stable and Co/Ni-Free O₃-layered Metal Oxide Cathode,” Advanced Materials 27, no. 43 (2015): 6928-6933.

RIGHTS & PERMISSIONS

2025 The Author(s). Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.