Unveiling Lithium-ion Migration Mechanisms in Anti-perovskite Solid Electrolytes: A Combined EIS and EDS Study of Defect Dynamics

Massoudi, Abouzar

doi:10.30501/acp.2026.584755.1198

Unveiling Lithium-ion Migration Mechanisms in Anti-perovskite Solid Electrolytes: A Combined EIS and EDS Study of Defect Dynamics

Document Type : Original Research Article

Author

Abouzar Massoudi

Associate Professor, Department of Semiconductors, Materials and Energy Research Center (MERC), P.O. Box 14155/4777, Karaj, Iran.

10.30501/acp.2026.584755.1198

Abstract

Understanding the defect-mediated migration mechanisms in solid electrolytes is critical for optimizing lithium-ion conductivity. This study investigates Li⁺ transport in lithium halide hydroxide anti-perovskite materials by systematically correlating defect structures with electrochemical performance. Samples with controlled compositions of 〖"Li" 〗_2 ("OH" )_(1-x) "F" _x "Cl (x=0.005)" were synthesized to stabilize orthorhombic, cubic, and Ruddlesden–Popper (RP) structural phases. To investigate ion transport mechanisms and elemental shifts during thermal cycling, EIS and EDS techniques were employed. EIS analysis revealed distinct activation energies associated with specific migration mechanisms: low-temperature transport in the RP and cubic phases was governed by Li⁺ vacancy or interstitial dumbbell migration, whereas high-temperature regimes were dominated by Schottky defect formation in LiCl or Li₂O. Complementary EDS findings indicated an increase in oxygen vacancies post-cycling, thereby corroborating the hypothesis regarding Schottky pair generation. Furthermore, high grain boundary resistance was attributed to excessive barriers arising from hydrogen-related defects. These findings provide a mechanistic framework for designing low-resistance solid-state electrolytes through the control of defect chemistry.

Keywords

Solid-State BatteriesLithium-Ion ConductivityDefect ChemistryRuddlesden&ndash

Popper PhasesElectrochemical Impedance Spectroscopy

Subjects

Lithium ion Batteries

1. Braga, M., Ferreira, J. A., Stockhausen, V., Oliveira, J., & El-Azab, A. (2014). Novel Li 3 ClO based glasses with superionic properties for lithium batteries. Journal of Materials Chemistry A, 2(15), 5470-5480. https://doi.org/10.1039/c3ta15087a

2. Braga, M. H., Stockhausen, V., Oliveira, J. C., & Ferreira, J. A. (2013). The role of defects in Li3ClO solid electrolyte: Calculations and experiments. MRS Online Proceedings Library, 1526(1), 1-5. https://doi.org/10.1557/opl.2013.519

3. Dawson, J., Famprikis, T., & Johnston, K. E. (2021). Anti-perovskites for solid-state batteries: recent developments, current challenges and future prospects. Journal of Materials Chemistry A, 9, 18746-18772. https://doi.org/10.1039/D1TA03680G

4. Dawson, J. A., Chen, H., & Islam, M. S. (2018). Composition screening of lithium-and sodium-rich anti-perovskites for fast-conducting solid electrolytes. The Journal of Physical Chemistry C, 122(42), 23978-23984. https://doi.org/10.1021/acs.jpcc.8b08208

5. Deng, Z., Ni, D., Chen, D., Bian, Y., Li, S., Wang, Z., & Zhao, Y. (2022). Anti‐perovskite materials for energy storage batteries. InfoMat, 4(2), e12252. https://doi.org/10.1002/inf2.12252

6. Gao, L., Zhang, X., Zhu, J., Han, S., Zhang, H., Wang, L., Zhao, R., Gao, S., Li, S., & Wang, Y. (2023). Boosting lithium ion conductivity of antiperovskite solid electrolyte by potassium ions substitution for cation clusters. Nature Communications, 14(1), 6807. https://doi.org/10.1038/s41467-023-42385-1

7. Guo, L., Xin, C., Gao, J., Zhu, J., Hu, Y., Zhang, Y., Li, J., Fan, X., Li, Y., & Li, H. (2021). The electrolysis of anti‐perovskite Li2OHCl for prelithiation of high‐energy‐density batteries. Angewandte Chemie, 133(23), 13123-13130. https://doi.org/10.1002/anie.202102605

8. Hanghofer, I., Redhammer, G. J., Rohde, S., Hanzu, I., Senyshyn, A., Wilkening, H. M. R., & Rettenwander, D. (2018). Untangling the Structure and Dynamics of Lithium-Rich Anti-Perovskites Envisaged as Solid Electrolytes for Batteries. Chemistry of materials, 30(22), 8134-8144. https://doi.org/10.1021/acs.chemmater.8b02568

9. Jaradat, T. e., & Khatib, T. (2025). A review of battery energy storage system for renewable energy penetration in electrical power system: Environmental impact, sizing methods, market features, and policy frameworks. Future Batteries, 7, 100106. https://doi.org/10.1016/j.fub.2025.100106

10. Koedtruad, A., Patino, M. A., Ichikawa, N., Kan, D., & Shimakawa, Y. (2020). Crystal structures and ionic conductivity in Li2OHX (X= Cl, Br) antiperovskites. Journal of Solid State Chemistry, 286, 121263. https://doi.org/10.1016/j.jssc.2020.121263

11. Li, Y., Zhou, W., Xin, S., Li, S., Zhu, J., Lü, X., Cui, Z., Jia, Q., Zhou, J., & Zhao, Y. (2016). Fluorine‐doped antiperovskite electrolyte for all‐solid‐state lithium‐ion batteries. Angewandte Chemie International Edition, 55(34), 9965-9968. https://doi.org/10.1002/anie.201604554

12. Lu, Z., Chen, C., Baiyee, Z. M., Chen, X., Niu, C., & Ciucci, F. (2015). Defect chemistry and lithium transport in Li3OCl anti-perovskite superionic conductors. Physical Chemistry Chemical Physics, 17(48), 32547-32555. https://doi.org/10.1039/c5cp05722a

13. Luo, Q., Liu, C., Li, L., Jiang, Z., Yang, J., Chen, S., Chen, X., Zhang, L., Cheng, S., & Yu, C. (2024). O-doping strategy enabling enhanced chemical/electrochemical stability of Li3InCl6 for superior solid-state battery performance. Journal of Energy Chemistry, 99, 484-494. https://doi.org/10.1016/j.jechem.2024.07.058

14. Moghadami, M., Massoudi, A., & Nangir, M. (2024). Unveiling the recent advances in micro-electrode materials and configurations for sodium-ion micro-batteries. Journal of Materials Chemistry A. https://doi.org/10.1039/D4TA02096K

15. Nangir, M., Massoudi, A., & Omidvar, H. (2023). Super Ionic Li3-2xMx(OH)1-yNyCl (M=Ca, W, N=F) Halide Hydroxide as an Anti-Perovskite Electrolyte for Solid-State Batteries. Journal of The Electrochemical Society, 170, 089001. http://iopscience.iop.org/article/10.1149/1945-7111/acdcbd

16. Nangir, M., Massoudi, A., & Omidvar, H. (2024). Role of hybrid solid state interface as a scavenger for anomalous Li dendrites in the lithium metal battery. Journal of Energy Storage, 99, 113360. https://doi.org/10.1016/j.est.2024.113360

17. Nangir, M., Massoudi, A., & Omidvar, H. (2025). Surface modification of lithium metal anode using polar polymer-in-ceramic electrolytes by grafting of anti-perovskite for inhibition dendrite growth. Journal of Energy Storage, 107, 114984. https://doi.org/10.1016/j.est.2024.114984

18. Qian, L., Ye, Y., Chen, D., Ni, D., Lin, H., Wang, X., Wu, L., Han, S., Zhu, J., & Zhao, Y. (2026). Sulfur-Doped Li2OHCl Antiperovskite Electrolyte for Stabilizing the Solid Electrolyte Interphase in Solid-State Lithium-Metal Batteries. ACS Energy Letters. https://doi.org/10.1021/acsenergylett.6c00619.s001

19. Shang, R., Nelson, T., Nguyen, T. V., Nelson, C., Antony, H., Abaoag, B., Ozkan, M., & Ozkan, C. S. (2025). A Comprehensive Review of Solid-State Lithium Batteries: Fast Charging Characteristics and In-Operando Diagnostics. Nano Energy, 111232. https://doi.org/10.1016/j.nanoen.2025.111232

20. Stegmaier, S., Voss, J., Reuter, K., & Luntz, A. C. (2017). Li+ defects in a solid-state Li ion battery: theoretical insights with a Li3OCl electrolyte. Chemistry of materials, 29(10), 4330-4340. https://doi.org/10.1021/acs.chemmater.7b00659

21. Sugumar, M. K., Yamamoto, T., Motoyama, M., & Iriyama, Y. (2020). Room temperature synthesis of anti-perovskite structured Li2OHBr. Solid State Ionics, 349, 115298. https://doi.org/10.1016/j.ssi.2020.115298

22. Wu, M., Xu, B., Lei, X., Huang, K., & Ouyang, C. (2018). Bulk properties and transport mechanisms of a solid state antiperovskite Li-ion conductor Li 3 OCl: insights from first principles calculations. Journal of Materials Chemistry A, 6(3), 1150-1160. https://doi.org/10.1039/c7ta08780b

23. Yan, Y., Zhang, S., Man, X., Li, Q., Xue, H., Xiao, P., Shi, Y., Yin, L., & Wang, R. (2026). Emerging inorganic amorphous solid-state electrolytes in all-solid-state lithium batteries: From crystallographic order to atomic and lattice disorder. eScience, 100531.

24. Ye, Y., Deng, Z., Gao, L., Niu, K., Zhao, R., Bian, J., Li, S., Lin, H., Zhu, J., & Zhao, Y. (2021). Lithium-Rich Anti-perovskite Li2OHBr-Based Polymer Electrolytes Enabling an Improved Interfacial Stability with a Three-Dimensional-Structured Lithium Metal Anode in All-Solid-State Batteries. ACS applied materials & interfaces, 13(24), 28108-28117. https://doi.org/10.1021/acsami.1c04514

25. Yin, L., Yuan, H., Kong, L., Lu, Z., & Zhao, Y. (2020). Engineering Frenkel defects of anti-perovskite solid-state electrolytes and their applications in all-solid-state lithium-ion batteries. Chemical Communications, 56(8), 1251-1254. https://doi.org/10.1039/c9cc08382k

26. Zhao, S., Chen, C., Li, H., & Zhang, W. (2021). Theoretical insights into the diffusion mechanism of alkali ions in Ruddlesden–Popper antiperovskites. New Journal of Chemistry, 45(9), 4219-4226. https://doi.org/10.1039/d0nj04850j

27. Zheng, J., Perry, B., & Wu, Y. (2021). Antiperovskite superionic conductors: a critical review. ACS Materials Au, 1(2), 92-106. https://doi.org/10.1021/acsmaterialsau.1c00026