Efficient Stepwise Screening of Inorganic Crystal Structure Databases for Novel Potassium-Ion Conducting Chalcogenides

Abstract

Potassium-conducting chalcogenides are attracting increasing attention as solid-state conducting materials for potassium-ion batteries. In this study, Inorganic Crystal Structure Database screening was performed for the first time to select new promising potassium-ion conductors among ternary and quaternary sulfides and selenides. From over 853 compounds studied, using a geometrical-topological analysis of free crystal space, we harvested 541 structures previously unreported as conductive materials in which periodic 1D, 2D, or 3D potassium migration maps were realized. Subsequently, the migration energy of the working cations was calculated for these structures using the bond valence site energy method, which allowed the selection of 37 structures with migration barriers below 1 eV, enabling 2D or 3D migration, and characterized by high crystal chemical stability. Kinetic Monte Carlo modeling then discovered nine structures with ionic conductivity exceeding 10⁻⁶ S⋅cm⁻¹ under standard conditions. For three ordered structures, K₆CdSe₄, K₃GeS₃, and K₄SnSe₄ with the highest ionic conductivities, DFT nudged elastic band simulations revealed 3D conductivity maps with migration barriers below 0.35 eV. According to ab initio molecular dynamics simulations, all three compounds exhibited ionic conductivity exceeding 10⁻⁵ S⋅cm⁻¹ at 300 K. Dependencies between migration barriers and parameters of conduction channels were also revealed in the series of isostructural compounds.

Keywords

chalcogenide / database / potassium-ion battery / topology

References

[1] M. Li, C. Wang, C. Wang, et al., “10 Years Development of Potassium-Ion Batteries,” Advanced Materials 37, no. 46 (2025): 2416717, https://doi.org/10.1002/adma.202416717.

[2] T. Masese and G. M. Kanyolo, “Inorganic Solid-State Electrolytes in Potassium Batteries: Advances, Challenges, and Future Prospects,” Chemelectrochem 12, no. 5 (2025): e202400598, https://doi.org/10.1002/celc.202400598.

[3] Z. Mao, K. Wang, Q. H. Fan, and R. Wang, “Advancements and Perspectives on Nonaqueous Electrolyte Engineering for Graphite Anode in Potassium-Ion Battery,” Small 21, no. 11 (2025): 2412419, https://doi.org/10.1002/smll.202412419.

[4] K. Cao, J. Ma, Z. Yue, H. Li, Y. Fan, and H. Liu, “Status and Challenges of Solid-State Electrolytes for Potassium Batteries,” Small 22, no. 12 (2025): 2500762, https://doi.org/10.1002/smll.202500762.

[5] S. Kim, M. Jang, and S. Yu, “Rational Materials Design for Stable Interfaces in All-Solid-State Potassium-Ion Batteries,” Journal of Materials Chemistry A 13, no. 45 (2025): 39013–39020, https://doi.org/10.1039/D5TA07134H.

[6] S. Yi, W. Zhou, Z. Wang, M. Yang, J.-F. Wu, and J. Liu, “Layered K₂Mg₂TeO₆ Solid Electrolyte Enables Long-Life Solid-State Potassium Batteries,” ACS Energy Letters 9, no. 6 (2024): 2626–2632, https://doi.org/10.1021/acsenergylett.4c00994.

[7] G. V Nechaev and E. I. Burmakin, “Potassium-Conducting Solid Electrolytes in K_{1 − 2x} Sr_X GaO₂ System,” Russian Journal of Electrochemistry 47, no. 12 (2011): 1411–1414, https://doi.org/10.1134/S1023193511120081.

[8] S. Ben Yahya and B. Louati, “Characterization of the Structure and Conduction Behavior of Overlapping Polaron Tunnel of Dipotassium Zinc Orthogermanate,” Journal of Alloys and Compounds 876 (2021): 159972, https://doi.org/10.1016/j.jallcom.2021.159972.

[9] E. Wang and M. Greenblatt, “Ionic Conductivity of Potassium Phosphatoantimonates and Some of Their Ion-Exchanged Analogs,” Chemistry of Materials 3, no. 3 (1991): 542–546, https://doi.org/10.1021/cm00015a034.

[10] I. D. Brown, “Recent Developments in the Methods and Applications of the Bond Valence Model,” Chemical Reviews 109, no. 12 (2009): 6858–6919, https://doi.org/10.1021/cr900053k.

[11] P. Schwerdtfeger and J. K. Nagle, “2018 Table of Static Dipole Polarizabilities of the Neutral Elements in the Periodic Table,” Molecular Physics 117, no. 9–12 (2019): 1200–1225, https://doi.org/10.1080/00268976.2018.1535143.

[12] J. Shao, J. Zheng, L. Qin, S. Zhang, Y. Ren, and Y. Wu, “K₃ SbS₄ as a Potassium Superionic Conductor With Low Activation Energy for K–S Batteries,” Angewandte Chemie 134, no. 20 (2022): e202200606, https://doi.org/10.1002/ange.202200606.

[13] J. Shao, H. Ao, L. Qin, et al., “Design and Synthesis of Cubic K_3−2xBa_xSbSe₄ Solid Electrolytes for K–O₂ Batteries,” Advanced Materials 35, no. 48 (2023): 2306809, https://doi.org/10.1002/adma.202306809.

[14] R. A. Eremin, N. A. Kabanova, Y. A. Morkhova, A. A. Golov, and V. A. Blatov, “High-Throughput Search for Potential Potassium Ion Conductors: A Combination of Geometrical-Topological and Density Functional Theory Approaches,” Solid State Ionics 326 (2018): 188–199, https://doi.org/10.1016/j.ssi.2018.10.009.

[15] Y. A. Morkhova, A. V Antonyuk, A. A. Kabanov, and V. A. Blatov, “A Set of New Promising Solid Chalcogenides for Na-Ion Batteries: Yield From the Crystal Chemical, Monte-Carlo and Quantum-Chemical Calculations,” ChemPhysChem 25, no. 18 (2024): e202400067, https://doi.org/10.1002/cphc.202400067.

[16] Y. Li, N. A. Kabanova, V. A. Blatov, and J. Wang, “High-Throughput Screening of Phosphide Compounds for Potassium-Ion Conductive Cathode Application,” Journal of Materials Informatics 5, no. 2 (2025), https://doi.org/10.20517/jmi.2024.87.

[17] Y. A. Morkhova, V. T. Osipov, A. V Antonyuk, and I. A. Naugolnova, “Hierarchical Screening of ICSD to Search for New high-conductive solid-state Materials Among Mixed Polyanionic Oxohalides for Sodium-Ion Batteries,” Journal of Solid State Electrochemistry 29, no. 7 (2025): 3043–3050, https://doi.org/10.1007/s10008-025-06205-4.

[18] Y. A. Morkhova, A. V Antonyuk, and I. A. Naugolnova, “High-Throughput Search for New Solid-State Sodium-Conducting Materials Among Polyanionic Oxides,” Journal of Solid State Electrochemistry 28, no. 10 (2024): 3665–3671, https://doi.org/10.1007/s10008-024-05965-9.

[19] V. A. Blatov, G. D. Ilyushin, O. A. Blatova, N. A. Anurova, A. K. Ivanov-Schits, and L. N. Dem’yanets, “Analysis of Migration Paths in Fast-Ion Conductors With Voronoi–Dirichlet Partition,” Acta Crystallographica Section B 62, no. 6 (2006): 1010–1018, https://doi.org/10.1107/S0108768106039425.

[20] V. A. Blatov, A. P. Shevchenko, and D. M. Proserpio, “Applied Topological Analysis of Crystal Structures With the Program Package ToposPro,” Crystal Growth & Design 14, no. 7 (2014): 3576–3586, https://doi.org/10.1021/cg500498k.

[21] H. Chen, L. L. Wong, and S. Adams, “SoftBV – a Software Tool for Screening the Materials Genome of Inorganic Fast Ion Conductors,” Acta Crystallographica Section B 75, no. 1 (2019): 18–33, https://doi.org/10.1107/S2052520618015718.

[22] S. Adams and R. P. Rao, “High Power Lithium Ion Battery Materials by Computational Design,” Physica Status Solidi 208, no. 8 (2011): 1746–1753, https://doi.org/10.1002/pssa.201001116.

[23] L. L. Wong, H. Chen, and S. Adams, “Design of Fast Ion Conducting Cathode Materials for Grid-Scale Sodium-Ion Batteries,” Physical Chemistry Chemical Physics 19, no. 11 (2017): 7506–7523, https://doi.org/10.1039/C7CP00037E.

[24] Y. A. Morkhova, M. Rothenberger, T. Leisegang, S. Adams, V. A. Blatov, and A. A. Kabanov, “Computational Search for Novel Zn-Ion Conductors—A Crystallochemical, Bond Valence, and Density Functional Study,” Journal of Physical Chemistry C 125, no. 32 (2021): 17590–17599, https://doi.org/10.1021/acs.jpcc.1c02984.

[25] S. Adams, O. Moretzki, and E. Canadell, “Global Instability Index Optimizations for the Localization of Mobile Protons,” Solid State Ionics 168, no. 3–4 (2004): 281–290, https://doi.org/10.1016/j.ssi.2003.04.002.

[26] K. D. Miller and J. M. Rondinelli, “Testing the Limits of the Global Instability Index,” APL Materials 11, no. 10 (2023): 101108, https://doi.org/10.1063/5.0140480.

[27] A. A. Kabanov, Y. A. Morkhova, I. A. Bezuglov, and V. A. Blatov, “Computational Design of Materials for Metal-Ion Batteries,” in Comprehensive Inorganic Chemistry III (Elsevier, 2023), 404–429, https://doi.org/10.1016/B978-0-12-823144-9.00062-5.

[28] R. Xiao, H. Li, and L. Chen, “High-Throughput Design and Optimization of Fast Lithium Ion Conductors by the Combination of Bond-Valence Method and Density Functional Theory,” Scientific Reports 5, no. 1 (2015): 14227, https://doi.org/10.1038/srep14227.

[29] L. L. Wong, K. C. Phuah, R. Dai, H. Chen, W. S. Chew, and S. Adams, “Bond Valence Pathway Analyzer—An Automatic Rapid Screening Tool for Fast Ion Conductors Within softBV,” Chemistry of Materials 33, no. 2 (2021): 625–641, https://doi.org/10.1021/acs.chemmater.0c03893.

[30] P. Hein, B. O. H. Grope, J. Koettgen, S. Grieshammer, and M. Martin, “Kinetic Monte Carlo Simulations of Ionic Conductivity in Oxygen Ion Conductors,” Materials Chemistry and Physics 257 (2021): 123767, https://doi.org/10.1016/j.matchemphys.2020.123767.

[31] G. Kresse and J. Furthmüller, “Efficient Iterative Schemes for ab initio total-Energy Calculations Using a Plane-Wave Basis Set,” Physical Review B: Condensed Matter 54, no. 16 (1996): 11169–11186, https://doi.org/10.1103/PhysRevB.54.11169.

[32] J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized Gradient Approximation Made Simple,” Physical Review Letters 77, no. 18 (1996): 3865–3868, https://doi.org/10.1103/PhysRevLett.77.3865.

[33] L. Jiang, Y. Lu, C. Zhao, et al., “Building Aqueous K-ion Batteries for Energy Storage,” Nature Energy 4, no. 6 (2019): 495–503, https://doi.org/10.1038/s41560-019-0388-0.

[34] Y. Gu, M. Chen, and B. Zheng, “First-Principles Study on the Electronic, Magnetic, and Optical Properties of Ni_1-x Mn_X Fe₂ O₄,” Journal of Physics. Conference Series 3129, no. 1 (2025): 012047, https://doi.org/10.1088/1742-6596/3129/1/012047.

[35] H. JóNSSON, G. Mills, and K. W. Jacobsen, “Nudged Elastic Band Method for Finding Minimum Energy Paths of Transitions, Classical and Quantum Dynamics in Condensed Phase Simulations,” World Scientific (1998): 385–404, https://doi.org/10.1142/9789812839664_0016.

[36] T. Ogawa, K. Sato, K. Mori, et al., “Point-Defect Chemistry for Ionic Conduction in Solid Electrolytes With Isovalent Cation Mixing,” Journal of Materials Chemistry A 12, no. 45 (2024): 31173–31184, https://doi.org/10.1039/D4TA05684A.

[37] A. A. Kabanov, Y. A. Morkhova, V. Osipov, M. Rothenberger, T. Leisegang, and V. A. Blatov, “A Novel Class of Multivalent Ionic Conductors With the La₃CuSiS₇ Structure Type: Results of Stepwise ICSD Screening,” Physical Chemistry Chemical Physics 26, no. 3 (2024): 2622–2628, https://doi.org/10.1039/D3CP04510B.

[38] R. Xiao, H. Li, and L. Chen, “High-Throughput Computational Discovery of K₂CdO₂ as an Ion Conductor for Solid-State Potassium-Ion Batteries,” Journal of Materials Chemistry A 8, no. 10 (2020): 5157–5162, https://doi.org/10.1039/C9TA13105A.

[39] J. Huang, X. Cai, Y. Li, et al., “DFT Investigations of KTiOPO₄M_x (M = K, Na, and Li) Anodes for Alkali-Ion Battery,” Journal of Chemical Physics 156, no. 20 (2022): 204702, https://doi.org/10.1063/5.0090071.

[40] N. V Proskurnina, V. I. Voronin, G. S. Shekhtman, et al., “Ionic Conductivity in Ti-Doped KFeO₂: Experiment and Mathematical Modeling,” Journal of Physical Chemistry C 121, no. 39 (2017): 21128–21135, https://doi.org/10.1021/acs.jpcc.7b05164.

[41] A. Baktash, J. C. Reid, T. Roman, and D. J. Searles, “Diffusion of Lithium Ions in Lithium-Argyrodite Solid-State Electrolytes,” npj Computational Materials 6, no. 1 (2020): 162, https://doi.org/10.1038/s41524-020-00432-1.

[42] Y. Zhang, J.-D. Luo, H.-B. Yao, and B. Jiang, “Size Dependent lithium-ion Conductivity of Solid Electrolytes in Machine Learning Molecular Dynamics Simulations,” Artificial Intelligence Chemistry 2, no. 1 (2024): 100051, https://doi.org/10.1016/j.aichem.2024.100051.

[43] R. Zhang, S. Xu, L. Wang, et al., “Theoretical Study on Ion Diffusion Mechanism in W-Doped K₃SbS₄ as Solid-State Electrolyte for K-Ion Batteries,” Inorganic Chemistry 63, no. 15 (2024): 6743–6751, https://doi.org/10.1021/acs.inorgchem.4c00074.

[44] Z. Li, J. Li, C. Xie, K. Butler, F. Du, and Y. Xie, “Large-Scale Simulation Unveiled Superior Potassium-Based Solid Electrolyte With High Ionic Conductivity and Excellent Electrochemical Stability in M₅ YSi₄ O₁₂ (M = Li, K),” PRX Energy 4, no. 3 (2025): 033007, https://doi.org/10.1103/8wkh-238p.

[45] I. Nußbruch and S. Dehnen, “Synthesis and Structures of Compounds with Molecular, One-Dimensional, or Two-Dimensional Selenidocadmate Anions,” Zeitschrift für Anorganische und Allgemeine Chemie 644, no. 24 (2018): 1897–1901, https://doi.org/10.1002/zaac.201800387.

[46] H. Ben Yahia, K. Motohashi, A. Sakuda, and A. Hayashi, “Mechanochemical Synthesis and Structure of the Alkali Metal Magnesium Chalcogenide Na₆MgS₄,” Inorganic Chemistry 62, no. 26 (2023): 10440–10449, https://doi.org/10.1021/acs.inorgchem.3c01415.

[47] B. Eisenmann, E. Kieselbach, H. Schäfer, and H. Schrod, “Über Thio-, Selenido- und Telluridogermanate (III): Zur Kenntnis von K₆Ge₂S₆, K₆Ge₂Se₆ und Na₆Ge₂Te₆,” Zeitschrift für Anorganische und Allgemeine Chemie 516, no. 9 (1984): 49–54, https://doi.org/10.1002/zaac.19845160908.

[48] K. O. Klepp, “ChemInform Abstract: Na4Snse4 and K4SnSe4, Two New Selenostannates With Discrete Anions,” ChemInform 23, no. 23 (1992): chin.199223017, https://doi.org/10.1002/chin.199223017.

[49] F. Kamm, F. Pielnhofer, and A. Pfitzner, “Sodium Selenotetrelates With Isolated TtSe₄-Tetrahedra (Tt = Si, Ge, Sn): Synthesis, Crystal Structures, Thermal Behavior, DFT Modeling, and Na Ion Conductivities,” Chemistry of Materials 36, no. 11 (2024): 5643–5650, https://doi.org/10.1021/acs.chemmater.4c00670.

[50] J. Zheng, H. Fang, L. Fan, Y. Ren, P. Jena, and Y. Wu, “Antiperovskite K₃OI for K-Ion Solid State Electrolyte,” Journal of Physical Chemistry Letters 12, no. 30 (2021): 7120–7126, https://doi.org/10.1021/acs.jpclett.1c01807.

Rights & permissions

2026 The Author(s). Materials Genome Engineering Advances published by Wiley-VCH GmbH on behalf of University of Science and Technology Beijing.