Intrapore-Structuring Nanocolloids Mediating Solvation and Interfaces in Lithium Metal Batteries

Abstract

Li metal batteries (LMBs) offer high energy density but suffer from Li dendrite growth and unstable solid-electrolyte interphase (SEI). Beyond conventional liquid systems, nanocolloid electrolytes (NCEs) incorporating insoluble nanoparticles dispersed in liquid electrolytes have emerged to mediate Li⁺ solvation and SEI formation, which are key factors governing Li dendrite suppression. Nonetheless, their practical application has been limited by an intrinsic trade-off between nanoparticle surface area and colloidal stability. To address this limitation, we propose an intrapore-structuring strategy that enables facile Li⁺ transport and efficient SEI regulation. Incorporating well-ordered mesopores into SiO₂ nanobeads achieves high surface area while retaining dispersibility by alleviating interparticle attraction. The intrapore-structured NCE alleviates viscosity increase, enhances anion mediation at the interface, and thereby effectively suppresses Li dendrite growth while promoting the buildup of anion-derived SEI. The LMB employing the intrapore-structured NCE demonstrates cycling stability over 300 cycles at 70% capacity retention and fast-charging capability up to 3 C, far outperforming NCEs using nonporous nanobeads and 7 nm-sized nanoparticles. This work establishes intrapore-structuring as a new design principle for realizing the practical potential of NCEs in LMBs.

Keywords

anion-derived SEI / intrapore-structuring / lithium metal battery / nanocolloid electrolyte / solvation mediator

References

[1] X.-B. Cheng, R. Zhang, C.-Z. Zhao, and Q. Zhang, “Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review,” Chemical Reviews 117, no. 15 (2017): 10403..

[2] Y. Jie, S. Wang, S. Weng, et al., “Towards Long-Life 500 Wh kg⁻¹ Lithium Metal Pouch Cells via Compact Ion-Pair Aggregate Electrolytes,” Nature Energy 9, no. 8 (2024): 987.

[3] H. Kim, G. Jeong, Y.-U. Kim, J.-H. Kim, C.-M. Park, and H.-J. Sohn, “Metallic Anodes for Next Generation Secondary Batteries,” Chemical Society Reviews 42, no. 23 (2013): 9011..

[4] W. Xu, J. Wang, F. Ding, et al., “Lithium Metal Anodes for Rechargeable Batteries,” Energy & Environmental Science 7, no. 2 (2014): 513.

[5] K. Li, G. Yuan, Y. Zhou, et al., “Collaborative Hollow Porous Structure Design and N Doping to Achieve a Win-Win Situation of “Stable” and “Fast” Lithium Battery,” SusMat 5, no. 1 (2025): e257.

[6] C.-P. Yang, Y.-X. Yin, S.-F. Zhang, N.-W. Li, and Y.-G. Guo, “Accommodating Lithium Into 3D Current Collectors With a Submicron Skeleton Towards Long-Life Lithium Metal Anodes,” Nature Communications 6, no. 1 (2015): 8058..

[7] X. Ren, S. Chen, H. Lee, et al., “Localized High-Concentration Sulfone Electrolytes for High-Efficiency Lithium-Metal Batteries,” Chemistry 4, no. 8 (2018): 1877.

[8] X. Ren, L. Zou, X. Cao, et al., “Enabling High-Voltage Lithium-Metal Batteries Under Practical Conditions,” Joule 3, no. 7 (2019): 1662.

[9] Y. Jo, D. Jin, M. Lim, et al., “Structural and Chemical Evolutions of Li/Electrolyte Interfaces in Li-Metal Batteries: Tracing Compositional Changes of Electrolytes Under Practical Conditions,” Advanced Science 10, no. 2 (2023): 2204812.

[10] M. Lim, H. Chang, G. Kim, et al., “Interfacial Impacts of Diluent-Mediated Anion Conformational Changes in Locally Concentrated Ionic Liquid Electrolytes,” Energy Storage Materials 79 (2025): 104288.

[11] S. Eom, M. Park, B. Koo, et al., “Suppressing Organic Cation Reactivity in Locally Concentrated Ionic Liquid Electrolytes for Lithium Metal Batteries,” Energy Storage Materials 74 (2025): 103966.

[12] D. Ruan, Y. Wang, J. Guo, et al., “Oscillating Lithium Ion-Acceptor Fluorine-Donor Electrolytes for Practical Fast-Charging High-Energy Lithium Metal Pouch Cells,” Energy & Environmental Science 18, no. 12 (2025): 6224.

[13] J. Jang, C. Wang, G. Kang, et al., “Miniature Li+ Solvation by Symmetric Molecular Design for Practical and Safe Li-Metal Batteries,” Nature Energy 10, no. 4 (2025): 502.

[14] H. Kwon, H. Kim, J. Hwang, et al., “Borate-Pyran Lean Electrolyte-Based Li-Metal Batteries With Minimal Li Corrosion,” Nature Energy 9, no. 1 (2024): 57.

[15] G. A. Giffin, “The Role of Concentration in Electrolyte Solutions for Non-Aqueous Lithium-Based Batteries,” Nature Communications 13, no. 1 (2022): 5250..

[16] T. Chen, J. You, R. Li, et al., “Ultra-Low Concentration Electrolyte Enabling LiF-Rich SEI and Dense Plating/Stripping Processes for Lithium Metal Batteries,” Advanced Science 9, no. 28 (2022): 2203216.

[17] O. Borodin, J. Self, K. A. Persson, C. Wang, and K. Xu, “Uncharted Waters: Super-Concentrated Electrolytes,” Joule 4, no. 1 (2020): 69.

[18] M. Lim, J. Seo, B. Choi, et al., “Intelligent Nano-Colloidal Electrolytes for Stabilizing Lithium Metal Anodes: A Review,” ChemElectroChem 11, no. 12 (2024): e202300621.

[19] A. Jarosik, C. Pfaffenhuber, A. Bunde, and J. Maier, “Electrochemical Investigations of Polyethylene Glycol-Based “Soggy Sand” Electrolytes—From the Local Mechanism to the Overall Conduction,” Advanced Functional Materials 21, no. 20 (2011): 3961.

[20] J. L. Schaefer, D. A. Yanga, and L. A. Archer, “High Lithium Transference Number Electrolytes via Creation of 3-Dimensional, Charged, Nanoporous Networks From Dense Functionalized Nanoparticle Composites,” Chemistry of Materials 25, no. 6 (2013): 834.

[21] J. Kim, D. G. Lee, J. H. Lee, et al., “Concurrent Electrode-Electrolyte Interfaces Engineering via Nano-Si₃N₄ Additive for High-Rate, High-Voltage Lithium Metal Batteries,” Energy & Environmental Science 18, no. 7 (2025): 3148.

[22] M. S. Kim, Z. Zhang, P. E. Rudnicki, et al., “Suspension Electrolyte With Modified Li+ Solvation Environment for Lithium Metal Batteries,” Nature Materials 21, no. 4 (2022): 445.

[23] Z. Ju, T. Zheng, A. C. Marschilok, E. S. Takeuchi, K. J. Takeuchi, and G. Yu, “Regulating Solvation Chemistries via Electric-Field-Induced Locally Concentrated Suspension Electrolytes for Lithium Metal Batteries,” Advanced Materials n/a, no. 40 (2025): e08743.

[24] J. Wu, X. Li, Z. Rao, et al., “Electrolyte With Boron Nitride Nanosheets as Leveling Agent Towards Dendrite-Free Lithium Metal Anodes,” Nano Energy 72 (2020): 104725.

[25] X. He, W. Hao, Z. Shi, et al., “Colloid Electrolyte Containing Li 3 P Nanoparticles for Highly Stable 4.7 V Lithium Metal Batteries,” ACS Nano 18, no. 33 (2024): 22560.

[26] X.-B. Cheng, M.-Q. Zhao, C. Chen, et al., “Nanodiamonds Suppress the Growth of Lithium Dendrites,” Nature Communications 8, no. 1 (2017): 336.

[27] L. Shen, H. B. Wu, F. Liu, et al., “Particulate Anion Sorbents as Electrolyte Additives for Lithium Batteries,” Advanced Functional Materials 30, no. 49 (2020): 2003055.

[28] S. Bai, Y. Sun, J. Yi, Y. He, Y. Qiao, and H. Zhou, “High-Power Li-Metal Anode Enabled by Metal-Organic Framework Modified Electrolyte,” Joule 2, no. 10 (2018): 2117.

[29] W. Zhang, G. Jiang, W. Zou, et al., “A Microscopically Heterogeneous Colloid Electrolyte of Covalent Organic Nanosheets for Ultrahigh-Voltage and Low-Temperature Lithium Metal Batteries,” Energy & Environmental Science 17, no. 7 (2024): 2642.

[30] M. Lim, H. An, J. Seo, et al., “Modulating Ionic Transport and Interface Chemistry via Surface-Modified Silica Carrier in Nano Colloid Electrolyte for Stable Cycling of Li-Metal Batteries,” Small 19, no. 43 (2023): 2302722.

[31] Y.-H. Tan, G.-X. Lu, J.-H. Zheng, et al., “Lithium Fluoride in Electrolyte for Stable and Safe Lithium-Metal Batteries,” Advanced Materials 33, no. 42 (2021): 2102134.

[32] M. S. Kim, Z. Zhang, J. Wang, et al., “Revealing the Multifunctions of Li₃N in the Suspension Electrolyte for Lithium Metal Batteries,” ACS Nano 17, no. 3 (2023): 3168.

[33] H. Xu, H. Li, L. Xie, D. Zhao, and B. Kong, “Interfacial Assembly of Functional Mesoporous Carbon-Based Materials Into Films for Batteries and Electrocatalysis,” Advanced Materials Interfaces 9, no. 10 (2022): 2101998.

[34] Y. He, R. Li, H. Tong, et al., “Emerging Compositions in Functional Mesoporous Materials,” Chemical Society Reviews 54, no. 14 (2025): 6927.

[35] V. Rabolli, L. C. J. Thomassen, F. Uwambayinema, J. A. Martens, and D. Lison, “The Cytotoxic Activity of Amorphous Silica Nanoparticles Is Mainly Influenced by Surface Area and not by Aggregation,” Toxicology Letters 206, no. 2 (2011): 197..

[36] P. Borm, F. C. Klaessig, T. D. Landry, et al., “Research Strategies for Safety Evaluation of Nanomaterials, Part V: Role of Dissolution in Biological Fate and Effects of Nanoscale Particles,” Toxicological Sciences 90, no. 1 (2006): 23.

[37] V. Valmacco, M. Elzbieciak-Wodka, C. Besnard, P. Maroni, G. Trefalt, and M. Borkovec, “Dispersion Forces Acting Between Silica Particles Across Water: Influence of Nanoscale Roughness,” Nanoscale Horizons 1, no. 4 (2016): 325..

[38] F. Meru, R. J. Geretshauser, C. Schäfer, R. Speith, and W. Kley, “Growth and Fragmentation of Centimetre-Sized Dust Aggregates: The Dependence on Aggregate Size and Porosity,” Monthly Notices of the Royal Astronomical Society 435, no. 3 (2013): 2371.

[39] H. Ohshima, “Chapter 9 - DLVO Theory of Colloid stability,” in Interface Science and Technology, ed. Ohshima, H. (Elsevier, 2024), 217.

[40] S. K. Das and A. J. Bhattacharyya, “Influence of Oxide Particle Network Morphology on Ion Solvation and Transport in “Soggy Sand” Electrolytes,” Journal of Physical Chemistry B 114, no. 20 (2010): 6830..

[41] C. Li, Q. Li, Y. V. Kaneti, D. Hou, Y. Yamauchi, and Y. Mai, “Self-Assembly of Block Copolymers Towards Mesoporous Materials for Energy Storage and Conversion Systems,” Chemical Society Reviews 49, no. 14 (2020): 4681..

[42] M. Ban, D. Woo, J. Hwang, S. Kim, and J. Lee, “Spinodal Decomposition-Driven Structural Hierarchy of Mesoporous Inorganic Materials for Energy Applications,” Accounts of Chemical Research 56, no. 23 (2023): 3428..

[43] T. Hashimoto, H. Tanaka, and H. Hasegawa, “Ordered Structure in Mixtures of a Block Copolymer and Homopolymers. 2. Effects of Molecular Weights of Homopolymers,” Macromolecules 23, no. 20 (1990): 4378.

[44] J. Hwang, S. Kim, U. Wiesner, and J. Lee, “Generalized Access to Mesoporous Inorganic Particles and Hollow Spheres From Multicomponent Polymer Blends,” Advanced Materials 30, no. 27 (2018): 1801127.

[45] D. Woo, M. Ban, J. Lee, et al., “Anisotropic Lens-Shaped Mesoporous Carbon From Interfacially Perpendicular Self-Assembly for Potassium-Ion Batteries,” Chemical Communications 60, no. 5 (2024): 590.

[46] J. Lee, H.-S. Lim, X. Cao, et al., “Lithium Dendrite Suppression With a Silica Nanoparticle-Dispersed Colloidal Electrolyte,” ACS Applied Materials & Interfaces 12, no. 33 (2020): 37188.

[47] Q. Han, Z. P. J. Candiloro, X. Cai, et al., “Silica Nanoparticle-Protein Aggregation and Protein Corona Formation Investigated With Scattering Techniques,” ACS Applied Materials & Interfaces 17, no. 5 (2025): 8574.

[48] L. O. Valøen and J. N. Reimers, “Transport Properties of LiPF6-Based Li-Ion Battery Electrolytes,” Journal of the Electrochemical Society 152, no. 5 (2005): A882.

[49] H. Wang, Z. Yu, X. Kong, et al., “Liquid Electrolyte: The Nexus of Practical Lithium Metal Batteries,” Joule 6, no. 3 (2022): 588.

[50] E. R. Logan and J. R. Dahn, “Electrolyte Design for Fast-Charging Li-Ion Batteries,” Trends in Chemistry 2, no. 4 (2020): 354.

[51] K. M. Diederichsen, E. J. Mcshane, and B. D. Mccloskey, “Promising Routes to a High Li⁺ Transference Number Electrolyte for Lithium Ion Batteries,” ACS Energy Letters 2, no. 11 (2017): 2563.

[52] P. Liang, H. Hu, Y. Dong, et al., “Competitive Coordination of Ternary Anions Enabling Fast Li-Ion Desolvation for Low-Temperature Lithium Metal Batteries,” Advanced Functional Materials 34, no. 16 (2024): 2309858.

[53] S. H. Lee, J.-Y. Hwang, J. Ming, et al., “Toward the Sustainable Lithium Metal Batteries With a New Electrolyte Solvation Chemistry,” Advanced Energy Materials 10, no. 20 (2020): 2000567.

[54] Y. Peng, K. Nishikawa, and K. Kanamura, “Effects of Carbonate Solvents and Lithium Salts in High-Concentration Electrolytes on Lithium Anode,” Journal of the Electrochemical Society 169, no. 6 (2022): 060548.

[55] E. W. C. Spotte-Smith, T. B. Petrocelli, H. D. Patel, S. M. Blau, and K. A. Persson, “Elementary Decomposition Mechanisms of Lithium Hexafluorophosphate in Battery Electrolytes and Interphases,” ACS Energy Letters 8, no. 1 (2023): 347.

[56] M. Xu, L. Zhou, L. Hao, L. Xing, W. Li, and B. L. Lucht, “Investigation and Application of Lithium Difluoro(Oxalate)Borate (LiDFOB) as Additive to Improve the Thermal Stability of Electrolyte for Lithium-Ion Batteries,” Journal of Power Sources 196, no. 16 (2011): 6794.

[57] B. Thirumalraj, T. T. Hagos, C.-J. Huang, et al., “Nucleation and Growth Mechanism of Lithium Metal Electroplating,” Journal of the American Chemical Society 141, no. 46 (2019): 18612.

[58] R. Weber, M. Genovese, A. J. Louli, et al., “Long Cycle Life and Dendrite-Free Lithium Morphology in Anode-Free Lithium Pouch Cells Enabled by a Dual-Salt Liquid Electrolyte,” Nature Energy 4, no. 8 (2019): 683.

[59] S. Ghosh, J. Dutta, K. K. Garlapati, et al., “LiF/Li_xPO_y/Li_xPO_yF_z-Based Artificial Interface on Graphitic Cathode for Improving the Cycle Life of Dual Ion Batteries,” Journal of Power Sources 623 (2024): 235440.

[60] X. Wang, M. Zhang, J. Alvarado, et al., “New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM,” Nano Letters 17, no. 12 (2017): 7606.

[61] Z. L. Brown and B. L. Lucht, “Synergistic Performance of Lithium Difluoro(Oxalato)Borate and Fluoroethylene Carbonate in Carbonate Electrolytes for Lithium Metal Anodes,” Journal of the Electrochemical Society 166, no. 3 (2019): A5117.

[62] G. Zhang, T. Zhang, Z. Zhang, et al., “High-Energy and Fast-Charging Lithium Metal Batteries Enabled by Tuning Li+-Solvation via Electron-Withdrawing and Lithiophobicity Functionality,” Nature Communications 16, no. 1 (2025): 4722.

[63] M. Lim, S. Kim, J. Kang, et al., “Dynamic Ionic Transport Actuated by Nanospinbar-Dispersed Colloidal Electrolytes Toward Dendrite-Free Electrodeposition,” Advanced Functional Materials 32, no. 40 (2022): 2204052.

[64] P. G. Bruce and C. A. Vincent, “Steady State Current Flow in Solid Binary Electrolyte Cells,” Journal of Electroanalytical Chemistry and Interfacial Electrochemistry 225, no. 1-2 (1987): 1.

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