High-Safety Lithium Metal Batteries Enabled by Additive of Fire-Extinguishing Microcapsules

Abstract

Lithium metal battery (LMB) is regarded as one of the most promising high-energy energy storage systems. However, the high reactivity of lithium metal and the formation of lithium dendrites during battery operation have caused safety concerns. Herein, we present the design and synthesis of fire-extinguishing microcapsules to enhance LMB safety. The encapsulation strategy addressed perfluoro(2-methyl-3-pentanone)’s volatility and storage challenges, yielding microcapsules with stable and uniform size distributions. The rapid release and effective fire-extinguishing performance of the microcapsules upon exposure to high temperatures has been demonstrated. Integration of these microcapsules into LMBs showed no significant impact on electrochemical performance, maintaining high lithium-ion conductivity, and stable cycling capacity. Notably, practical safety tests on pouch cells indicated that the presence of microcapsules effectively prevented ignition and improved thermal stability under mechanical damage and flame intrusion, underscoring their potential for significantly improved battery safety. These findings provide a robust strategy for mitigating fire hazards of high-energy-density battery systems without compromising their electrochemical performances.

Keywords

electrochemical performances / fire extinguishing / lithium metal battery / microcapsules / safety

References

[1] B. Dunn, H. Kamath, and J. M. Tarascon, “Electrical Energy Storage for the Grid: A Battery of Choices,” Science 334 (2011):928–935.

[2] J. Y. Wang, R. S. Chen, L. F. Yang, et al., “Rasing the Intrinsic Safty of Layered Oxide Cathodes by Surface Re-Lithination With LLZTO Garnet-Type Solid Electrolytes,” Advanced Materials 34 (2022):2200655.

[3] Y. Chen, Y. Y. Cui, S. M. Wang, et al., “Durable and Adjustable Interfacial Engineering of Polymeric Electrolytes for Both Stable Ni-Rich Cathodes and High-Energy Metal Anodes,” Advanced Materials 35 (2023):2300982.

[4] N. Khossossi, W. Luo, Z. Haman, et al., “Revealing the Superlative Electrochemical Properties of o-B2N2 Monolayer in Lithium/Sodium-Ion Batteries,” Nano Energy 96 (2022):107066.

[5] W. W. Sun, S. K. Liu, Y. J. Li, et al., “Monodispersed FeS2 Electrocatalyst Anchored to Nitrogen-Doped Carbon Host for Lithium-Sulfur Baterries,” Advanced Functional Materials 32 (2022):2205471.

[6] C. H. Jo, K. S. Sohn, and S. T. Myung, “Feasible Approaches for Anode-Free Lithium-Metal Batteries as Next Generation Energy Storage Systems,” Energy Storage Materials 57 (2023):471–496.

[7] T. Kim, “Hybrid Artificial Cathode-Electrolyte Interphase Stimulation Layer (A-CEISL) to Simultaneously Improve Stability and Safety for Lithium Metal Batteries,” Nano Energy 120 (2024):109177.

[8] Y. Zheng, W. Zhang, J. Gui, et al., “Two-in-One Structure as Both Lithium Protective Layer and Electrolyte for Safe Solid-State Lithium-Metal Battery,” Energy Storage Materials 61 (2023):102884.

[9] L. P. Hou, X. Q. Zhang, B. Q. Li, and Q. Zhang, “Cycling a Lithium Metal Anode at 90°C in a Liquid Electrolyte,” Angewandte Chemie International Edition 59 (2020):15109–15113.

[10] Q. Zhou, S. M. Dong, Z. L. Lv, et al., “A Temperature-Responsive Electrolyte Endowing Superior Safety Characterristic of Lithium Metal Batteries,” Advanced Engineering Materials 10 (2020):1903441.

[11] D. L. Chen, M. Zhu, P. B. Kang, et al., “Self-Enhancing Gel Polymer Electrolyte by In Situ Constrictuction for Enabling Safe Lithium Metal Battery,” Advanced Science 9 (2022):2103663.

[12] Z. Zhang and W. Q. Han, “From Liquid to Solid-State Lithium Metal Batteries: Fundamental Issues and Recent Developments,” Nano-Micro Letters 16 (2024):24.

[13] W. Ren, Y. Zheng, Z. Cui, Y. Tao, B. Li, and W. Wang, “Recent Progress of Functional Separators in Dendrite Inhibition for Lithium Metal Batteries,” Energy Storage Materials 35 (2021):157–168.

[14] L. T. Gao, Y. Lyu, and Z. S. Guo, “External Pressure Affecting Dendrite Growth and Dissolution in Lithium Metal Batteries During Cycles,” ACS Applied Materials &Interfaces 15 (2023):58416–58428.

[15] S. J. Tan, J. Yue, Y. F. Tian, et al., “In-Situ Encapsulating Flame-Retardant Phosphate Into Robust Polymer Matrix for Safe and Stable Quasi-Solid-State Lithium Metal Batteries,” Energy Storage Materials 39 (2021):186–193.

[16] Y. Y. Mao, T. J. Zhu, X. Q. Hao, et al., “Growth Mechanism for Dendrite-Free Lithium Regulated Deposition,” Journal of Energy Storage 77 (2024):109904.

[17] W. Mu, X. Liu, Z. Wen, and L. Liu, “Numerical Simulation of the Factors Affecting the Growth of Lithium Dendrites,” Journal of Energy Storage 26 (2019):100921.

[18] F. N. Jiang, S. J. Yang, X. B. Cheng, et al., “Thermal Safety of Dendritic Lithium Against Non-Aqueous Electrolyte in Pouch-Type Lithium Metal Batteries,” Journal of Energy Chemistry 72 (2022):158–165.

[19] C. Zu, J. Li, B. Cai, et al., “Separators With Reactive Metal Oxide Coatings for Dendrite-Free Lithium Metal Anodes,” Journal of Power Sources 555 (2023):232336.

[20] Z. Zeng, V. Murugesan, K. S. Han, et al., “Non-Flammable Electrolytes With High Salt-to-Solvent Ratios for Li-Ion and Li-Metal Batteries,” Nature Energy 3 (2018):674–681.

[21] J. Chen, Z. Yang, G. Liu, et al., “Reinforcing Concentrated Phosphate Electrolytes With In-Situ Polymerized Skeletons for Robust Quasi-Solid Lithium Metal Batteries,” Energy Storage Materials 25 (2020):305–312.

[22] X. D. Lin, J. Yu, M. B. Effat, et al., “Ultrathin and Non-Flammable Dual-Salt Polymer Electrolyte for High-Energy-Density Lithium-Metal Battery,” Advanced Functional Materials 31 (2021):2010261.

[23] C. Liao, L. F. Han, W. Wang, et al., “Non-Flammable Electrolyte With Lithium Nitrate as the Only Lithium Salt for Boosting Ultra-Stable Cycling and Fire-Safety Lithium Metal Batteries,” Advanced Functional Materials 33 (2023):2212605.

[24] T. D. Pham, A. Bin Faheem, J. Kim, K. Kwak, and K. K. Lee, “Non-Flammable Electrolytes Based on a Fluorine-Free Salt for Safe and High-Voltage Lithium Metal Batteries,” Electrochimica Acta 458 (2023):142496.

[25] S. J. Tan, J. P. Yue, Z. Chen, et al., “Ester-Enhanced Inorganic-Rich Solid Electrolyte Interphase Enabled Dendrite-Free Fast-Charging Lithium Metal Batteries,” Energy Material Advances 5 (2024):0076.

[26] S. J. Tan, Y. F. Tian, Y. Zhao, et al., “Noncoordinating Flame-Retardant Functional Electrolyte Solvents for Rechargeable Lithium-Ion Batteries,” Journal of the American Chemical Society 144 (2022):18240–18245.

[27] H. Li, F. Wang, C. Zhang, et al., “A Temperature-Sensitive Poly(3-Octylpyrrole)/Carbon Composite as a Conductive Matrix of Cathodes for Building Safer Li-Ion Batteries,” Energy Storage Materials 17 (2019):275–283.

[28] T. Li, L. Wang, and J. Li, “A Safer Organic Cathode Material With Overheating Self-Protection Function for Lithium Batteries,” Chemical Engineering Journal 431 (2022):133901.

[29] X. Zhang, C. Zhang, H. Li, Y. Cao, H. Yang, and X. Ai, “Reversible Temperature-Responsive Cathode for Thermal Protection of Lithium-Ion Batteries,” ACS Applied Energy Materials 5 (2022):5236–5244.

[30] J. Zhang and Y. Mu, “A Schiff Based p-Phenylenediimine Polymer as High Capacity Anode Materials for Stable Lithium Ion Batteries,” Electrochimica Acta 450 (2023):142276.

[31] Y. Zhong, Y. Chen, Y. Cheng, et al., “Li Alginate-Based Artificial SEI Layer for Stable Lithium Metal Anodes,” ACS Applied Materials & Interfaces 11 (2019):37726–37731.

[32] J. Zeng, Q. Liu, D. Jia, et al., “A Polymer Brush-Based Robust and Flexible Single-Ion Conducting Artificial Sei Film for Fast Charging Lithium Metal Batteries,” Energy Storage Materials 41 (2021):697–702.

[33] W. Cao, J. Lu, K. Zhou, et al., “Organic-Inorganic Composite Sei for a Stable Li Metal Anode by In-Situ Polymerization,” Nano Energy 95 (2022):106983.

[34] M. Zhou, Y. Liao, L. Li, et al., “Unraveling the Heterogeneity of Solid Electrolyte Interphase Kinetically Affecting Lithium Electrodeposition on Lithium Metal Anode,” Journal of Energy Chemistry 85 (2023):181–190.

[35] K. Wang, P. Y. Wang, Y. Qian, et al., “Enabling High-Performance Sodium Metal Anodes by 2D Nanomaterials Engineering: A Review,” Materials Today Energy 42 (2024):101565.

[36] S. J. Tan, J. Yue, X. C. Hu, et al., “Nitriding-Interface-Regulated Lithium Plating Enables Flame-Retardant Electrolytes for High-Voltage Lithium Metal Batteries,” Angewandte Chemie 131 (2019):7884–7889.

[37] R. Pan, R. Sun, Z. Wang, et al., “Sandwich-Structured Nano/Micro Fiber-Based Separators for Lithium Metal Batteries,” Nano Energy 55 (2019):316–326.

[38] Q. Zhao, R. K. Zhou, C. J. Wang, et al., “Anion Immobilization Enabled by Cation-Selective Separators for Dendrite-Free Lithium Metal Batteries,” Advanced Functional Materials 32 (2022):2112711.

[39] D. M. D Babiker, Z. R. Usha, C. Wan, et al., “A Polyolefin-Based Hybrid Separator for Durable and Advanced Lithium-/Sodium-Metal Batteries,” Journal of Energy Storage 73 (2023):108888.

[40] P. Li, Z. Liu, Y. Peng, et al., “Fast Thermal Responsive Separators Toward Long-Life and Safe Lithium Metal Batteries,” Nano Research 17 (2024):2746–2754.

[41] X. Zhu, H. Wang, X. Wang, et al., “Internal Short Circuit and Failure Mechanisms of Lithium-Ion Pouch Cells Under Mechanical Indentation Abuse Conditions: An Experimental Study,” Journal of Power Sources 455 (2020):227939.

[42] Y. Liu, Y. Mao, H. Wang, Y. Pan, and B. Liu, “Internal Short Circuit of Lithium Metal Batteries Under Mechanical Abuse,” International Journal of Mechanical Sciences 245 (2023):108130.

[43] S. C. Zhang, S. Y. Li, X. Y. Wang, et al., “Nonflammable Electrolyte With Low Exthermic Design for Safer Lithium-Based Batteries,” Nano Energy 114 (2023):108639.

[44] W. Li, U. H. Kim, A. Dolocan, Y. K. Sun, and A. Manthiram, “Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover,” ACS Nano 11 (2017):5853–5863.

[45] W. Ji, H. Huang, X. Zhang, et al., “A Redox-Active Organic Salt for Safer Na-Ion Batteries,” Nano Energy 72 (2020):104705.

[46] B. Mosallanejad, S. S. Malek, M. Ershadi, et al., “Cycling Degradation and Safety Issues in Sodium-Ion Batteries: Promises of Electrolyte Additives,” Journal of Electroanalytical Chemistry 895 (2021):115505.

[47] H. Wu, Z. Song, W. Feng, Z. Zhou, and H. Zhang, “Lithium (Fluorosulfonyl)(n-Nonafluorobutanesulfonyl)Imide for Stabilizing Cathode–Electrolyte Interface in Sulfonamide Electrolytes,” Nano Research 16 (2023):9507–9518.

[48] M. Zhu, J. Wu, Y. Wang, et al., “Recent Advances in Gel Polymer Electrolyte for High-Performance Lithium Batteries,” Journal of Energy Chemistry 37 (2019):126–142.

[49] X. H. Zhang, L. Huang, B. Xie, et al., “Deciphering the Thermal Failure Mechanism of Anode-Free Lithium Metal Pouch Batteries,” Advanced Engineering Materials 13 (2023):2203648.

[50] X. B. Cheng, S. J. Yang, Z. C. Liu, et al., “Electrochemically and Thermally Stable Inorganic-Rich Solid Electrolyte Interphase for Roubust Lithium Metal Batteries,” Advanced Materials 36 (2024):2307370.

[51] Z. Cui, Z. Jia, D. Ruan, et al., “Molecular Anchoring of Free Solvents for High-Voltage and High-Safety Lithium Metal Batteries,” Nature Communications 15 (2024):2033.

[52] B. Yang, Y. Pan, T. Li, et al., “High-Safety Lithium Metal Pouch Cells for Extreme Abuse Conditions by Implementing Flame-Retardant Perfluorinated Gel Polymer Electrolytes,” Energy Storage Materials 65 (2024):103124.

[53] R. R. Li, Z. H. Liu, S. Q. Zheng, et al., “Trifunctional Composite Thermal Barrier Mitigates the Thermal Runaway Propagation of Large-Format Prismatic Lithium-Ion Batteries,” Journal of Energy Storage 73 (2023):109178.

[54] L. Wang, C. Wang, X. Lu, et al., “A Design for a Lithium-Ion Battery Pack Monitoring System Based on NB-IoT-ZigBee,” Electronics 12 (2023):3561.

[55] J. Close, J. E. Barnard, Y. M. John Chew, and S. Perera, “A Holistic Approach to Improving Safety for Battery Energy Storage Systems,” Journal of Energy Chemistry 92 (2024):422–439.

[56] Y. Zheng, Y. Che, X. Hu, X. Sui, D. I. Stroe, and R. Teodorescu, “Thermal State Monitoring of Lithium-Ion Batteries: Progress, Challenges, and Opportunities,” Progress in Energy and Combustion Science 100 (2024):101120.

[57] P. Yan, Y. Zhu, X. Pan, and H. Ji, “A Novel Flame-Retardant Electrolyte Additive for Safer Lithium-Ion Batteries,” International Journal of Energy Research 45 (2021):2776–2784.

[58] C. Z. Zhang, L. J. Xie, Y. Tang, Y. Li, J. C. Jiang, and A. C. Huang, “Thermal Safety Evaluation of Silane Polymer Compounds as Electrolyte Additives for Silicon-Based Anode Lithium-Ion Batteries,” Processes 10 (2022):1581.

[59] M. C. Liu, Q. S. Liu, Y. Z. Quan, et al., “Phosphorus-Silicon-Integrated Electrolyte Additive Boosts Cycling Performance and Safety of High-Voltage Lithium-Ion Batteries,” Chinese Chemical Letters 35 (2024):109123.

[60] B. Andersson and P. Blomqvist, “Experimental Study of Thermal Breakdown Products From Halogenated Extinguishing Agents,” Fire Safety Journal 46 (2011):104–115.

[61] N. Tao, Y. Cheng, H. R. Xing, S. M. Lo, S. Lu, and H. P. Zhang. “Thermal Decomposition and Fire-Extinguishing Mechanism of N(CF₂CF₃),” International Journal of Quantum Chemistry 122 (2022):e26898.

[62] W. Liu, F. Zhao, M. Kong, S. Yin, H. Wang, and X. Liu, “Reaction Mechanism of Lithium-Ion Battery Fire Extinguishing Agent-Perfluorinated Hexanone Oxidizes Metal-Al,” Fire Technology 58 (2022):2811–2823.

[63] C. Xue, H. Jiang, C. Zhu, and W. Gao, “A Novel Dry Water With Perfluorohexanone for Explosion Suppression of AlH3,” Chemical Engineering Science 271 (2023):118575.

[64] Y. Wang, Y. Chen, W. Dai, et al., “Anisotropic Black Phosphorene Structural Modulation for Thermal Storage and Solar-Thermal Conversion (Small 52/2023),” Small 19 (2023):2303344.

[65] D. Y. Zhang, Y. R. Xue, X. C. Zheng, C. Zhang, and Y. L. Li. “Multi-Heterointerfaces for Selective and Efficient Urea Production,” National Science Review 10 (2023):209.

[66] Y. Ren, D. Yuan, W. Li, and X. Cai, “Flame Retardant Efficiency of KH-550 Modified Urea-Formaldehyde Resin Cooperating With Ammonium Polyphosphate on Polypropylene,” Polymer Degradation and Stability 151 (2018):160–171.

[67] D. H. Lee, S. Kwon, Y. E. Kim, N. Y. Kim, and J. B. Joo, “Double-Layered Polymer Microcapsule Containing Non-Flammable Agent for Initial Fire Suppression,” Materials 15 (2022):7831.

[68] T. W. Zhang, H. Liu, J. W. Song, et al., “Synergistic Inhibition Effect on Lithium-Ion Batteries During Thermal Runway by N₂-Twin-Fluid Liquid Mist,” Case Studies in Thermal Engineering 37 (2022):102269.

[69] C. Li, H. Bian, D. Ding, F. Huang, and Z. Zhu, “Enhancing Safety in Small Confined Spaces With Thermally Triggered Fire-Extinguishing Microcapsules From Microfluidics,” Lab on a Chip 24 (2024):904–912.

[70] W. Xu, Y. Jiang, R. Qiu, and X. Ren, “Influence of Halon Replacements on Laminar Flame Speeds and Extinction Limits of Hydrocarbon Flames,” Combustion and Flame 182 (2017):1–13.

[71] L. Liu, Z. Du, T. Zhang, Z. Guo, M. He, and Z. Liu, “The Inhibition/Promotion Effect of C6F12O Added to a Lithium-Ion Cell Syngas Premixed Flame,” International Journal of Hydrogen Energy 44 (2019):22282–22300.

[72] H. Liu, T. W. Zhang, M. Zhang, et al., “Preparation and Thermal Responsiveness of Microencapsulated Fluorinated Liquids for Automatic Fire Extinguishing,” Heliyon 10 (2024):e27454.

[73] T. Yim, M. S. Park, S. G. Woo, et al., “Self-Extinguishing Lithium Ion Batteries Based on Internally Embedded Fire-Extinguishing Microcapsules With Temperature-Responsiveness,” Nano Letters 15 (2015):5059–5067.

[74] A. Latnikova, D. O. Grigoriev, H. Möhwald, and D. G. Shchukin, “Capsules Made of Cross-Linked Polymers and Liquid Core: Possible Morphologies and Their Estimation on the Basis of Hansen Solubility Parameters,” Journal of Physical Chemistry C 116 (2012):8181–8187.

[75] O. Galant, M. Davidovich-Pinhas, and C. E. Diesendruck, “The Effect of Intramolecular Cross-Linking on Polymer Interactions in Solution,” Macromolecular Rapid Communications 39 (2018):1800407.

[76] Q. Zhang, X. Cui, S. Hao, et al., “Chain Engineering of Carbonyl Polymers for Sustainable Lithium-Ion Batteries,” Materials Today 50 (2021):170–198.

RIGHTS & PERMISSIONS

2024 The Author(s). Carbon Neutralization published by Wenzhou University and John Wiley & Sons Australia, Ltd.