Crystalline Structure Engineering of Metal Sulfides Toward Advanced Sodium-Ion Storage

Abstract

Transition metal sulfides (TMSs) have garnered significant attention due to their unique physiochemical properties and high theoretical capacities. However, their poor intrinsic electronic conductivity hinders reaction kinetics. In this study, we propose a strategy of crystalline structure engineering to achieve metallic electronic conductivity, thereby significantly enhancing the electrochemical reaction kinetics during sodium-ion storage. Our findings reveal that iron sulfides with different crystal structures exhibit distinct electrochemical behaviors in sodium-ion batteries. Specifically, the metallic-phase tetragonal FeS, characterized by its layered structure, demonstrates superior electronic conductivity, electrochemical reversibility, and fast reaction kinetics. These attributes result in a markedly higher sodium storage capacity and faster electrochemical reactivity compared to semiconducting hexagonal FeS. This study introduces a critical strategy for designing next-generation sodium storage anodes with improved electrochemical performance.

Keywords

crystalline structure engineering / metal sulfides / reaction kinetics / sodium-ion battery

References

[1] S. Wu, Y. Chen, W. Luan, et al., “A Review of Multiscale Mechanical Failures in Lithium-Ion Batteries: Implications for Performance, Lifetime and Safety,” Electrochemical Energy Reviews 7 (2024): 35.

[2] J. Wang, J. Li, Q. Zhang, et al., “Rational-Designed High-Performance Anode Materials for Sodium-Ion Batteries: A Review,” Advanced Composites and Hybrid Materials 7 (2024): 119.

[3] L. Duan, Y. Zhang, H. Tang, J. Liao, G. Zhou, and X. Zhou. “Recent Advances in High-Entropy Layered Oxide Cathode Materials for Alkali Metal-Ion Batteries,” Advanced Materials 37 (2024): 2411426.

[4] P. Geng, S. Zheng, H. Tang, et al., “Transition Metal Sulfides Based on Graphene for Electrochemical Energy Storage,” Advanced Energy Materials 8 (2018): 1703259.

[5] Z. Hu, Q. Liu, S. L. Chou, and S. X. Dou. “Advances and Challenges in Metal Sulfides/Selenides for Next-Generation Rechargeable Sodium-Ion Batteries,” Advanced Materials 29 (2017): 1700606.

[6] Y. V. Lim, X. L. Li, and H. Y. Yang. “Recent Tactics and Advances in the Application of Metal Sulfides as High-Performance Anode Materials for Rechargeable Sodium-Ion Batteries,” Advanced Functional Materials 10 (2020): 31.

[7] L. Shen, Y. Wang, F. Wu, et al., “Hierarchical Metal Sulfide/Carbon Spheres: A Generalized Synthesis and High Sodium-Storage Performance,” Angewandte Chemie International Edition 58 (2019): 7238–7243.

[8] W. Zhao, X. Ma, G. Wang, et al., “Significantly Enhanced Ion-Migration and Sodium-Storage Capability Derived by Strongly Coupled Dual Interfacial Engineering in Heterogeneous Bimetallic Sulfides With Densified Carbon Matrix,” SusMat 4 (2024): e198.

[9] Y. Fang, X. Y. Yu, and X. W. Lou, “Bullet-Like Cu₉S₅Hollow Particles Coated With Nitrogen-Doped Carbon for Sodium-Ion Batteries,” Angewandte Chemie International Edition 58 (2019): 7744–7748.

[10] Z. Song, G. Wang, Y. Chen, Q. Chang, Y. Lu, and Z. Wen. “Construction of Hierarchical NiS@ C/rGO Heterostructures for Enhanced Sodium Storage,” Chemical Engineering Journal 435 (2022): 134633.

[11] Y. Li, L. Zhang, X. Wang, et al., “High Capacity and Superior Rate Performances Coexisting in Carbon-Based Sodium-Ion Battery Anode,” Research: A Journal of Science and Its Applications 2019 (2019): 6930294.

[12] Y. Luo, L. Shi, H. He, G. Cong, C. Zhu, and J. Xu, “Rationally Designed Yolk–Shell Co₉S₈–Co_1−xS Hollow Spheres for Advanced Sodium-Ion Storage,” Journal of Materials Chemistry A 9 (2021): 23537–23544.

[13] B. Wang, K. Qian, X. Jiao, et al., “Metal Doping and Vacancy Synergistic Induced Electron/Ion Engineering to Optimize the Redox Kinetics of Sodium Storage: A Case Study Mo_1-xW_xSe₂,” Energy Storage Materials 63 (2023): 102998.

[14] Y. Wang, Y. Chen, L. Chen, et al., “Cobalt-Doped MoS₂ Coated Polyaniline Composites as Superior Anode Materials for High-Performance Lithium-Ion Batteries,” Journal of Energy Storage 76 (2024): 109803.

[15] X. Wen, W. Feng, X. Li, et al., “Diatomite-Templated Synthesis of Single-Atom Cobalt-Doped MoS₂/Carbon Composites to Boost Sodium Storage,” Advanced Materials 35 (2023): 2211690.

[16] B. Chen, D. Chao, E. Liu, M. Jaroniec, N. Zhao, and S.-Z. Qiao. “Transition Metal Dichalcogenides for Alkali Metal Ion Batteries: Engineering Strategies at the Atomic Level,” Energy & Environmental Science 13 (2020): 1096.

[17] X. Ma, W. Zhang, Y. Deng, C. Zhong, W. Hu, and X. Han, “Phase and Composition Controlled Synthesis of Cobalt Sulfide Hollow Nanospheres for Electrocatalytic Water Splitting,” Nanoscale 10 (2018): 4816–4824.

[18] J. Wu, S. Liu, Y. Rehman, et al., “Phase Engineering of Nickel Sulfides to Boost Sodium-and Potassium-Ion Storage Performance,” Advanced Functional Materials 31 (2021): 2010832.

[19] J. Sun, Z. Zhao, J. Li, Z. Li, and X. Meng. “Recent Advances in Transition Metal Selenides-Based Electrocatalysts: Rational Design and Applications in Water Splitting,” Journal of Alloys and Compounds 918 (2022): 165719.

[20] Z. Lu and B. Zhu, “ Crystal Structure Prediction for Battery Materials,” in Computational Design of Battery Materials, eds. D. A. H. Hanaor. (Topics in Applied Physics, 2024).

[21] J.-W. Zhao, H.-Y. Wang, L. Feng, J.-Z. Zhu, J.-X. Liu, and W.-X. Li, “Crystal-Phase Engineering in Heterogeneous Catalysis,” Chemical Reviews 124 (2023): 164–209.

[22] H. Chen, M. Zhang, Y. Wang, et al., “Crystal Phase Engineering of Electrocatalysts for Energy Conversions,” Nano Research 15 (2022): 10194–10217.

[23] C. Wang, Y. Zhang, J. Huang, et al., “Observation of Fermi arc and Its Connection With Bulk States in the Candidate Type-II Weyl Semimetal WTe₂,” Physical Review B 94 (2016): 241119.

[24] Q. Yuan, Y. Chen, A. Li, et al., “Polysulfides Anchoring and Enhanced Electrochemical Kinetics of 3D Flower-Like FeS/Carbon Assembly Materials for Lithium-Ssulfur Battery,” Applied Surface Science 508 (2020): 145286.

[25] X. Lai, H. Zhang, Y. Wang, et al., “Observation of Superconductivity in Tetragonal FeS,” Journal of the American Chemical Society 137 (2015): 10148–10151.

[26] H. Chen, X. Yang, P. Lv, P. Tian, S. Wan, and Q. Liu. “Mn-Doped FeS With Larger Lattice Spacing as Advance Anode for Sodium Ion Half/Full Battery,” Chemical Engineering Journal 450 (2022): 137960.

[27] D. Yang, W. Chen, X. Zhang, et al., “Facile and Scalable Synthesis of Low-Cost FeS@C as Long-Cycle Anodes for Sodium-Ion Batteries,” Journal of Materials Chemistry A 7 (2019): 19709–19718.

[28] X. Zhang, W. Weng, H. Gu, et al., “Versatile Preparation of Mesoporous Single-Layered Transition-Metal Sulfide/Carbon Composites for Enhanced Sodium Storage,” Advanced Materials 34 (2021): 2104427.

[29] H. Lim, S. Kim, J. Hoon Kim, et al., “Carbon Shell-Coated Mackinawite FeS Platelets as Anode Materials for High-Performance Sodium-Ion Batteries,” Chemical Engineering Journal 458 (2023): 141354.

[30] Y. Wang, Y. Chen, W. Dai, et al., “Engineering C-S-Fe Bond Confinement Effect to Stabilize Metallic-Phase Sulfide for High Power Density Sodium-Ion Batteries,” Small 19 (2023): 2302200.

[31] B.-H. Hou, Y.-Y. Wang, J.-Z. Guo, et al., “Pseudocapacitance-Boosted Ultrafast Na Storage in a Pie-Like FeS@C Nanohybrid as an Advanced Anode Material for Sodium-Ion Full Batteries,” Nanoscale 10 (2018): 9218–9225.

[32] Y. Zhao, X. Shi, S. J. H. Ong, et al., “Enhancing the Charge Transportation Ability of Yolk–Shell Structure for High-Rate Sodium and Potassium Storage,” ACS Nano 14 (2020): 4463–4474.

[33] Z. Cao, H. Song, B. Cao, et al., “Sheet-on-Sheet Chrysanthemum-Like C/FeS Microspheres Synthesized by One-Step Solvothermal Method for High-Performance Sodium-Ion Batteries,” Journal of Power Sources 364 (2017): 208–214.

[34] J. S. Cho, J.-S. Park, and Y. C. Kang, “Porous FeS Nanofibers With Numerous Nanovoids Obtained by Kirkendall Diffusion Effect for Use as Anode Materials for Sodium-Ion Batteries,” Nano Research 10 (2016): 897–907.

[35] D. Yuan, Y. Dou, Y. Tian, D. Adekoya, L. Xu, and S. Zhang, “Robust Pseudocapacitive Sodium Cation Intercalation Induced by Cobalt Vacancies at Atomically Thin Co_1−xSe₂/Graphene Heterostructure for Sodium-Ion Batteries,” Angewandte Chemie International Edition 60 (2021): 18830–18837.

[36] H. Yang, T. Bu, W. Liu, et al., “A Novel Triboelectric-Optical Hybrid Tactile Sensor for Human-Machine Tactile Interaction,” Nano Energy 125 (2024): 109592.

[37] T. Xu, Z. Li, D. Wang, et al., “A Fast Proton-Induced Pseudocapacitive Supercapacitor With High Energy and Power Density,” Advanced Functional Materials 32 (2021): 2107720.

[38] L. Wu, J. O. Yang, S. Guo, et al., “Pseudocapacitive Trimetal Fe_0.8CoMnO₄ Nanoparticles@Carbon Nanofibers as High-Performance Sodium Storage Anode With Self-Supported Mechanism,” Advanced Functional Materials 30 (2020): 2001718.

[39] C. Choi, D. S. Ashby, D. M. Butts, et al., “Achieving High Energy Density and High Power Density With Pseudocapacitive Materials,” Nature Reviews Materials 5 (2019): 5–19.

[40] K. Sugai, R. Tatsumi, M. Uehara, T. Kuramoto, and Y. Kimishima, “Intrinsic Pinning Property of NaFe₂Se₂ Superconductor,” Physics Procedia 58 (2014): 118–121.

[41] V. V. Bannikov, I. R. Shein, and A. L. Ivanovskii, “Trends in Structural, Electronic Properties and Fermi Surface Topology of 15 Tetragonal ThCr₂Si₂-Type Phases AFe₂Ch₂, Where A=Li, Na, K, Rb, and Cs; Ch=S, Se, and Te, as Parent Systems of New Ternary Iron–Chalcogenide Superconductors,” Computational Materials Science 60 (2012): 1–6.

[42] G. S. Henderson, F. M. F. de Groot, and B. J. A. Moulton, “X-Ray Absorption Near-Edge Structure (XANES) Spectroscopy,” Reviews in Mineralogy and Geochemistry 78 (2014): 75–138.

[43] A. Kitajou, J. Yamaguchi, S. Hara, and S. Okada, “Discharge/Charge Reaction Mechanism of a Pyrite-Type FeS₂ Cathode for Sodium Secondary Batteries,” Journal of Power Sources 247 (2014): 391–395.

[44] W. E. Jackson, F. Farges, M. Yeager, et al., “Multi-Spectroscopic Study of Fe(II) in Silicate Glasses: Implications for the Coordination Environment of Fe(II) in Silicate Melts,” Geochimica et Cosmochimica Acta 69 (2005): 4315–4332.

[45] X. Wang, S. Kajiyama, H. Iinuma, et al., “Pseudocapacitance of MXene Nanosheets for High-Power Sodium-Ion Hybrid Capacitors,” Nature Communications 6 (2015): 6544.

[46] J. Pan, S. Chen, D. Zhang, et al., “SnP₂O₇ Covered Carbon Nanosheets as a Long-Life and High-Rate Anode Material for Sodium-Ion Batteries,” Advanced Functional Materials 28 (2018): 1804672.

[47] N. Wang, Z. Bai, Y. Qian, and J. Yang, “Double-Walled Sb@TiO_2−xNanotubes as a Superior High-Rate and Ultralong-Lifespan Anode Material for Na-Ion and Li-Ion Batteries,” Advanced Materials 28 (2016): 4126–4133.

[48] Y. Ma, Y. Ma, H. Euchner, et al., “An Alternative Charge-Storage Mechanism for High-Performance Sodium-Ion and Potassium-Ion Anodes,” ACS Energy Letters 6 (2021): 915–924.

[49] Z. Chen, V. Augustyn, X. Jia, Q. Xiao, B. Dunn, and Y. Lu, “High-Performance Sodium-Ion Pseudocapacitors Based on Hierarchically Porous Nanowire Composites,” ACS Nano 6 (2012): 4319–4327.

[50] B. Xu, Y. Cao, J. Xu, D. Zhao, N. Wang, and B. Wang, “A New Nickel/Cobalt Borate as High-Performance Anode Material for Sodium-Ion Batteries,” Batteries & Supercaps 10 (2023): 6.

[51] X. Chen, L. Zhang, J. Cui, et al., “Semiconductor-to-Metal Transition Renders Intrinsic Pseudocapacitance and High Volumetric Capacity for Iron Chalcogenide Anode,” Chemical Engineering Journal 480 (2024): 147979.

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