Mechanical Stress-Tolerant Diffusion-Dependent Electrode With Well-Dispersed Silicon Particles for High-Performance All-Solid-State Batteries

Abstract

All-solid-state batteries (ASSBs) are a promising next-generation energy storage solution due to their high energy density and enhanced safety. To achieve this, specialized electrode designs are required to efficiently enhance interparticle lithium-ion transport between solid components. In particular, for active materials with high specific capacity, such as silicon, their volume expansion and shrinkage must be carefully controlled to maintain mechanical interface stability, which is crucial for effective lithium-ion transport in ASSBs. Herein, we propose a mechanical stress-tolerant all-solid-state graphite/silicon electrode design to ensure stable lithium-ion diffusion at the interface through morphology control of active material particles. Plate-type graphite with a high surface-area-to-volume ratio is used to maximize the dispersion of silicon within the electrode. The carefully designed electrode can accommodate the volume changes of silicon, ensuring stable capacity retention over cycles. Additionally, spherical graphite is shown to contribute to improved rate performance by providing an efficient lithium-ion diffusion pathway within the electrode. Therefore, the synergistic effect of our electrode structure offers balanced electrochemical performance, providing practical insights into the mechano–electrochemical interactions essential for designing high-performance all-solid-state electrodes.

Keywords

active material / all-solid-state electrode / electrode design / mechano–electrochemical interaction

References

[1] Q. Zhao, S. Stalin, C.-Z. Zhao, and L. A. Archer, “Designing Solid-State Electrolytes for Safe, Energy-Dense Batteries,” Nature Reviews Materials 5 (2020): 229-252.

[2] K. Takada, T. Ohno, N. Ohta, T. Ohnishi, and Y. Tanaka, “Positive and Negative Aspects of Interfaces in Solid-State Batteries,” ACS Energy Letters 3, no. 1 (2017): 98-103.

[3] J. Janek and W. G. Zeier, “A Solid Future for Battery Development,” Nature Energy 1, no. 9 (2016): 16141.

[4] 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.

[5] T. Ye, L. Li, and Y. Zhang, “Recent Progress in Solid Electrolytes for Energy Storage Devices,” Advanced Functional Materials 30, no. 29 (2020): 2000077.

[6] Z. Xie, X. Song, J. Cao, and S. Xu, “Energy Efficiency Task Scheduling for Battery Level-Aware Mobile Edge Computing in Heterogeneous Networks,” ETRI Journal 44, no. 5 (2022): 746-758.

[7] T. Liu, Y. Yuan, X. Tao, Z. Lin, and J. Lu, “Bipolar Electrodes for Next-Generation Rechargeable Batteries,” Advanced Science 7, no. 17 (2020): 2001207.

[8] Y. Zhu and Y. Mo, “Materials Design Principles for Air-Stable Lithium/Sodium Solid Electrolytes,” Angewandte Chemie International Edition 59, no. 40 (2020): 17472-17476.

[9] L. Zhou, K.-H. Park, X. Sun, et al., “Solvent-Engineered Design of Argyrodite Li₆PS₅X (X = Cl, Br, I) Solid Electrolytes With High Ionic Conductivity,” ACS Energy Letters 4, no. 1 (2019): 265-270.

[10] Y. Wang, W. D. Richards, S. P. Ong, et al., “Design Principles for Solid-State Lithium Superionic Conductors,” Nature Materials 14, no. 10 (2015): 1026-1031.

[11] H. Kwak, D. Han, J. Lyoo, et al., “New Cost-Effective Halide Solid Electrolytes for All-Solid-State Batteries: Mechanochemically Prepared Fe₃⁺-Substituted Li₂ZrCl₆,” Advanced Energy Materials 11, no. 12 (2021): 2003190.

[12] J. E. Lee, K.-H. Park, J. C. Kim, et al., “Universal Solution Synthesis of Sulfide Solid Electrolytes Using Alkahest for All-Solid-State Batteries,” Advanced Materials 34, no. 16 (2022): 2200083.

[13] H. Kwak, S. Wang, J. Park, et al., “Emerging Halide Superionic Conductors for All-Solid-State Batteries: Design, Synthesis, and Practical Applications,” ACS Energy Letters 7, no. 5 (2022): 1776-1805.

[14] J. Feng, Z. Gao, L. Sheng, Z. Hao, and F. R. Wang, “Progress and Perspective of Interface Design in Garnet Electrolyte-Based All-Solid-State Batteries,” Carbon Energy 3, no. 3 (2021): 385-409.

[15] Z. Shen, Y. Cheng, S. Sun, X. Ke, L. Liu, and Z. Shi, “The Critical Role of Inorganic Nanofillers in Solid Polymer Composite Electrolyte for Li⁺ Transportation,” Carbon Energy 3, no. 3 (2021): 482-508.

[16] S. Qin, Y. Cao, J. Zhang, et al., “Polymer Dispersed Ionic Liquid Electrolytes With High Ionic Conductivity for Ultrastable Solid-State Lithium Batteries,” Carbon Energy 5, no. 5 (2023): e316.

[17] J. Park, K. T. Kim, D. Y. Oh, et al., “Digital Twin-Driven All-Solid-State Battery: Unraveling the Physical and Electrochemical Behaviors,” Advanced Energy Materials 10, no. 35 (2020): 2001563.

[18] X. Chen, W. He, L.-X. Ding, S. Wang, and H. Wang, “Enhancing Interfacial Contact in All Solid State Batteries With a Cathode-Supported Solid Electrolyte Membrane Framework,” Energy & Environmental Science 12, no. 3 (2019): 938-944.

[19] W. Jiang, X. Zhu, R. Huang, et al., “Revealing the Design Principles of Ni-Rich Cathodes for All-Solid-State Batteries,” Advanced Energy Materials 12, no. 13 (2022): 2103473.

[20] J. Y. Kim, S. Jung, S. H. Kang, et al., “All-Solid-State Hybrid Electrode Configuration for High-Performance All-Solid-State Batteries: Comparative Study With Composite Electrode and Diffusion-Dependent Electrode,” Journal of Power Sources 518 (2022): 230736.

[21] J. Y. Kim, J. Park, M. J. Lee, et al., “Diffusion-Dependent Graphite Electrode for All-Solid-State Batteries With Extremely High Energy Density,” ACS Energy Letters 5, no. 9 (2020): 2995-3004.

[22] J. Y. Kim, S. Jung, S. H. Kang, et al., “Graphite-Silicon Diffusion-Dependent Electrode With Short Effective Diffusion Length for High-Performance All-Solid-State Batteries,” Advanced Energy Materials 12, no. 3 (2022): 2103108.

[23] J. Park, J. Y. Kim, D. O. Shin, et al., “Dimension-Controlled Solid Oxide Electrolytes for All-Solid-State Electrodes: Percolation Pathways, Specific Contact Area, and Effective Ionic Conductivity,” Chemical Engineering Journal 391 (2020): 123528.

[24] S. Wang, W. Zhang, X. Chen, et al., “Influence of Crystallinity of Lithium Thiophosphate Solid Electrolytes on the Performance of Solid-State Batteries,” Advanced Energy Materials 11, no. 24 (2021): 2100654.

[25] R. Koerver, I. Aygün, T. Leichtweiß, et al., “Capacity Fade in Solid-State Batteries: Interphase Formation and Chemomechanical Processes in Nickel-Rich Layered Oxide Cathodes and Lithium Thiophosphate Solid Electrolytes,” Chemistry of Materials 29, no. 13 (2017): 5574-5582.

[26] S. Zhou, M. Li, P. Wang, et al., “Liquid Metal as an Efficient Protective Layer for Lithium Metal Anodes in All-Solid-State Batteries,” Carbon Energy 6, no. 7 (2024): e462.

[27] A. L. Davis, V. Goel, D. W. Liao, et al., “Rate Limitations in Composite Solid-State Battery Electrodes: Revealing Heterogeneity With Operando Microscopy,” ACS Energy Letters 6, no. 8 (2021): 2993-3003.

[28] Y. J. Nam, D. Y. Oh, S. H. Jung, and Y. S. Jung, “Toward Practical All-Solid-State Lithium-Ion Batteries With High Energy Density and Safety: Comparative Study for Electrodes Fabricated by Dry- and Slurry-Mixing Processes,” Journal of Power Sources 375 (2018): 93-101.

[29] Y. S. Park, K. Kim, J.-W. Lee, J. Moon, H. Park, and H. Hwang, “Effect of Cell Pressure on the Electrochemical Performance of All-Solid-State Lithium Batteries With Zero-Excess Li Metal Anode,” Journal of the American Ceramic Society 106, no. 10 (2023): 7322-7330.

[30] C. Hänsel and D. Kundu, “The Stack Pressure Dilemma in Sulfide Electrolyte Based Li Metal Solid-State Batteries: A Case Study With Li₆PS₅Cl Solid Electrolyte,” Advanced Materials Interfaces 8, no. 10 (2021): 2100206.

[31] J.-M. Doux, H. Nguyen, D. H. S. Tan, et al., “Stack Pressure Considerations for Room-Temperature All-Solid-State Lithium Metal Batteries,” Advanced Energy Materials 10, no. 1 (2020): 1903253.

[32] M. Cronau, M. Szabo, C. König, T. B. Wassermann, and B. Roling, “How to Measure a Reliable Ionic Conductivity? The Stack Pressure Dilemma of Microcrystalline Sulfide-Based Solid Electrolytes,” ACS Energy Letters 6, no. 9 (2021): 3072-3077.

[33] K. Lee, J. Lee, S. Choi, K. Char, and J. W. Choi, “Thiol-Ene Click Reaction for Fine Polarity Tuning of Polymeric Binders in Solution-Processed All-Solid-State Batteries,” ACS Energy Letters 4, no. 1 (2018): 94-101.

[34] K. T. Kim, T. Y. Kwon, Y. B. Song, et al., “Wet-Slurry Fabrication Using PVDF-HFP Binder With Sulfide Electrolytes via Synergetic Cosolvent Approach for All-Solid-State Batteries,” Chemical Engineering Journal 450, no. 2 (2022): 138047.

[35] F. Hippauf, B. Schumm, S. Doerfler, et al., “Overcoming Binder Limitations of Sheet-Type Solid-State Cathodes Using a Solvent-Free Dry-Film Approach,” Energy Storage Materials 21 (2019): 390-398.

[36] R. Li, N. Chen, S. Liu, et al., “Finely-Tuned Polar-Nonpolar Synergistic Binder Enables Ultra-Thin Sulfide Solid Electrolyte Membrane for All-Solid-State Batteries,” Advanced Functional Materials 34, no. 49 (2024): 2409403.

[37] T. Y. Kwon, K. T. Kim, D. Y. Oh, Y. B. Song, S. Jun, and Y. S. Jung, “Three-Dimensional Networking Binders Prepared in Situ During Wet-Slurry Process for All-Solid-State Batteries Operating Under Low External Pressure,” Energy Storage Materials 49 (2022): 219-226.

[38] J. Choi, J. Y. Kim, S. H. Kang, D. O. Shin, M. J. Lee, and Y. G. Lee, “Revealing Interfacial Parasitic Reactions of Nitrile Rubber Binders in All-Solid-State Lithium Batteries,” Journal of Materials Chemistry A 12, no. 11 (2024): 6426-6437.

[39] B. Koo, H. Kim, Y. Cho, K. T. Lee, N. Choi, and J. Cho, “A Highly Cross-Linked Polymeric Binder for High-Performance Silicon Negative Electrodes in Lithium Ion Batteries,” Angewandte Chemie International Edition 51, no. 35 (2012): 8762-8767.

[40] K. Zaghib, X. Song, A. Guerfi, R. Rioux, and K. Kinoshita, “Purification Process of Natural Graphite as Anode for Li-Ion Batteries: Chemical Versus Thermal,” Journal of Power Sources 119-121 (2003): 8-15.

[41] N. Ogihara, Y. Itou, T. Sasaki, and Y. Takeuchi, “Impedance Spectroscopy Characterization of Porous Electrodes Under Different Electrode Thickness Using a Symmetric Cell for High-Performance Lithium-Ion Batteries,” Journal of Physical Chemistry C 119, no. 9 (2015): 4612-4619.

[42] N. Kaiser, S. Spannenberger, M. Schmitt, M. Cronau, Y. Kato, and B. Roling, “Ion Transport Limitations in All-Solid-State Lithium Battery Electrodes Containing a Sulfide-Based Electrolyte,” Journal of Power Sources 396 (2018): 175-181.

[43] J. Y. Kim, J. Park, S. H. Kang, et al., “Revisiting TiS₂ as a Diffusion-Dependent Cathode With Promising Energy Density for All-Solid-State Lithium Secondary Batteries,” Energy Storage Materials 41 (2021): 289-296.

[44] R. Tian, M. Breshears, D. V. Horvath, and J. N. Coleman, “The Rate Performance of Two-Dimensional Material-Based Battery Electrodes May Not Be as Good as Commonly Believed,” ACS Nano 14, no. 3 (2020): 3129-3140.

[45] S. Kim, H. Lee, J. Lim, J. Park, and Y. M. Lee, “Digital Twin Battery Modeling and Simulations: A New Analysis and Design Tool for Rechargeable Batteries,” ACS Energy Letters 9, no. 10 (2024): 5225-5239.

[46] J. W. Choi and D. Aurbach, “Promise and Reality of Post-Lithium-Ion Batteries With High Energy Densities,” Nature Reviews Materials 1 (2016): 16013.

[47] A. A. Wereszczak, K. Breder, M. K. Ferber, et al., “Dimensional Changes and Creep of Silica Core Ceramics Used in Investment Casting of Superalloys,” Journal of Materials Science 37, no. 19 (2002): 4235-4245.

[48] J. Billaud, F. Bouville, T. Magrini, C. Villevieille, and A. R. Studart, “Magnetically Aligned Graphite Electrodes for High-Rate Performance Li-Ion Batteries,” Nature Energy 1, no. 8 (2016): 16097.

[49] W. A. Dollase, “Correction of Intensities for Preferred Orientation in Powder Diffractometry: Application of the March Model,” Journal of Applied Crystallography 19, no. 4 (1986): 267-272.

[50] C. Huang, C. L. A. Leung, P. Leung, and P. S. Grant, “A Solid-State Battery Cathode With a Polymer Composite Electrolyte and Low Tortuosity Microstructure by Directional Freezing and Polymerization,” Advanced Energy Materials 11, no. 1 (2021): 2002387.

[51] G. Shao, D. A. H. Hanaor, X. Shen, and A. Gurlo, “Freeze Casting: From Low-Dimensional Building Blocks to Aligned Porous Structures—A Review of Novel Materials, Methods, and Applications,” Advanced Materials 32, no. 17 (2020): e1907176.

[52] K.-H. Chen, M. J. Namkoong, V. Goel, et al., “Efficient Fast-Charging of Lithium-Ion Batteries Enabled by Laser-Patterned Three-Dimensional Graphite Anode Architectures,” Journal of Power Sources 471 (2020): 228475.

[53] H. Huo, M. Jiang, Y. Bai, et al., “Chemo-Mechanical Failure Mechanisms of the Silicon Anode in Solid-State Batteries,” Nature Materials 23, no. 4 (2024): 543-551.

[54] L. Liu, J. Xu, S. Wang, F. Wu, H. Li, and L. Chen, “Practical Evaluation of Energy Densities for Sulfide Solid-State Batteries,” eTransportation 1 (2019): 100010.

[55] A. Kato, M. Nose, M. Yamamoto, A. Sakuda, A. Hayashi, and M. Tatsumisago, “Mechanical Properties of Sulfide Glasses in All-Solid-State Batteries,” Journal of the Ceramic Society of Japan 126, no. 9 (2018): 719-727.

[56] Y. Ren, C. Sun, J. Liu, G. Cai, X. Tan, and C. Zhang, “Effect of the Mechanical Strength on the Ion Transport in a Transition Metal Lithium Halide Electrolyte: First-Principle Calculations,” Materials Today Communications 33 (2022): 104570.

[57] C. G. Haslam, J. B. Wolfenstine, and J. Sakamoto, “The Effect of Aspect Ratio on the Mechanical Behavior of Li Metal in Solid-State Cells,” Journal of Power Sources 520 (2022): 230831.

[58] H.-T. Jeong and W. J. Kim, “Deformation Mechanism Maps of Pure Lithium: Their Application in Determining Stack Pressure for All-Solid-State Lithium-Ion Batteries,” ACS Energy Letters 9, no. 7 (2024): 3237-3251.

[59] H. Yan, K. Tantratian, K. Ellwood, et al., “How Does the Creep Stress Regulate Void Formation at the Lithium-Solid Electrolyte Interface During Stripping?,” Advanced Energy Materials 12, no. 2 (2021): 2102283.

RIGHTS & PERMISSIONS

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