Flowerlike CeO₂ used as novel adsorption material for removal of hydrogen fluoride gas from lithium-ion battery during thermal runaway

Abstract

Thermal runaway presents a significant challenge for large-scale application of lithium-ion batteries (LIBs), often leading to the release of flammable, explosive, and toxic gases. In this study, porous flowerlike cerium dioxide microspheres (FL-CeO₂) were investigated to eliminate hydrogen fluoride (HF) gas generated during thermal runaway. A dedicated test device and method were developed for this purpose. The FL-CeO₂ was synthesized via a hydrothermal method and coated onto nickel foam to fabricate a gas filter. During thermal runaway of a 5 Ah lithium iron phosphate (LiFePO₄) battery, the filter—loaded with 1.2 g CeO₂—achieved an instantaneous HF removal rate of up to 82.24% within approximately 40–50 s. X-ray photoelectron spectroscopy (XPS) results indicate that F⁻ ions replace O²⁻ ions in the CeO₂ lattice. Additionally, the potential for reusability of the CeO₂ microspheres was evaluated through multiple HF adsorption and desorption cycles. After 10 cycles, the regenerated CeO₂ microspheres retained a HF adsorption rate of 76.11%, demonstrating promising reusability.

Graphical abstract

Keywords

lithium-ion batteries (LIBs) / thermal runaway / ceria microspheres / hydrogen fluoride (HF) / regeneration

References

[1] Grey C P, Hall D S. Prospects for lithium-ion batteries and beyond—A 2030 vision. Nature Communications, 2020, 11(1): 6279

[2] ZhangX, Feng J, CaiF, et al. A novel state of health estimation model for lithium-ion batteries incorporating signal processing and optimized machine learning methods. Frontiers in Energy, 2024 , early access,doi:10.1007/s11708-024-0969-x

[3] Ding L, Chen Y, Sheng Y. . Eliminating hydrogen fluoride through piperidine-doped separators for stable Li metal batteries with nickel-rich cathodes. Angewandte Chemie International Edition, 2024, 63(51): e202411933

[4] Wang H, Xu H, Zhang Z. . Fire and explosion characteristics of vent gas from lithium-ion batteries after thermal runaway: A comparative study. eTransportation, 2022, 13: 100190

[5] Zhou W, Li G, Zhao H. . Experimental study of explosion parameters of hybrid mixture caused by thermal runaway of lithium-ion battery. Process Safety and Environmental Protection, 2023, 178: 872–880

[6] Wei G, Huang R, Zhang G. . A comprehensive insight into the thermal runaway issues in the view of lithium-ion battery intrinsic safety performance and venting gas explosion hazards. Applied Energy, 2023, 349: 121651

[7] Zhao L, Hou J, Feng X. . The trade-off characteristic between battery thermal runaway and combustion. Energy Storage Materials, 2024, 69: 103380

[8] Feng X, Ren D, He X. . Mitigating thermal runaway of lithium-ion batteries. Joule, 2020, 4(4): 743–770

[9] Wang Q, Mao B, Stoliarov S I. . A review of lithium ion battery failure mechanisms and fire prevention strategies. Progress in Energy and Combustion Science, 2019, 73: 95–131

[10] Larsson F, Bertilsson S, Furlani M. . Gasexplosions and thermal runaways during external heating abuse of commercia lithium-ion graphite-LiCoO₂ cells at different levels of ageing. Journal of Power Sources, 2018, 373: 220–231

[11] Bugryniec P J, Resendiz E G, Nwophoke S M. . Review of gas emissions from lithium-ion battery thermal runaway failure—Considering toxic and flammable compounds. Journal of Energy Storage, 2024, 87: 111288

[12] Claassen M, Bingham B, Chow J C. . Characterization of lithium-ion battery fire emissions—Part 1: Chemical composition of fine particles (PM_2.5). Batteries, 2024, 10(9): 301

[13] Claassen M, Bingham B, Chow J C. . Characterization of lithium-ion battery fire emissions—Part 2: Particle size distributions and emission factors. Batteries, 2024, 10(10): 366

[14] Yuan L, Dubaniewicz T, Zlochower I. . Experimental study on thermal runaway and vented gases of lithium-ion cells. Process Safety and Environmental Protection, 2020, 144: 186–192

[15] Qin P, Jia Z, Wu J. . The thermal runaway analysis on LiFePO₄ electrical energy storage packs with different venting areas and void volumes. Applied Energy, 2022, 313: 118767

[16] Larsson F, Andersson P, Blomqvist P. . Toxic fluoride gas emissions from lithium-ion battery fires. Scientific Reports, 2017, 7(1): 10018

[17] Zhang L, Duan Q, Meng X. . Experimental investigation on intermittent spray cooling and toxic hazards of lithium-ion battery thermal runaway. Energy Conversion and Management, 2022, 252: 115091

[18] Krebs R, Owens J, Luckarift H. Formation and detection of hydrogen fluoride gas during fire fighting scenarios. Fire Safety Journal, 2022, 127: 103489

[19] Yang H, Zhuang G V, Ross P N Jr. Thermal stability of LiPF₆ salt and Li-ion battery electrolytes containing LiPF₆. Journal of Power Sources, 2006, 161(1): 573–579

[20] Kawamura T, Okada S, Yamaki J. Decomposition reaction of LiPF₆-based electrolytes for lithium ion cells. Journal of Power Sources, 2006, 156(2): 547–554

[21] Larsson F, Andersson P, Blomqvist P. . Characteristics of lithium-ion batteries during fire tests. Journal of Power Sources, 2014, 271: 414–420

[22] Larsson F, Anderson J, Andersson P. . Thermal modelling of cell-to-cell fire propagation and cascading thermal runaway failure effects for lithium-ion battery cells and modules using fire walls. Journal of the Electrochemical Society, 2016, 163(14): A2854–A2865

[23] Kahya N, Erim F B. Removal of fluoride ions from water by cerium-carboxymethyl cellulose beads doped with CeO₂ nanoparticles. International Journal of Biological Macromolecules, 2023, 242: 124595

[24] Kang D, Yu X, Ge M. Morphology-dependent properties and adsorption performance of CeO₂ for fluoride removal. Chemical Engineering Journal, 2017, 330: 36–43

[25] Wang Y, Luo X. Efficient adsorptive removal of low concentration fluoride ions from water by cellulose beads with trapped CeO₂ nanoparticles. Journal of Environmental Chemical Engineering, 2024, 12(5): 113180

[26] Singh S K, Pahi S, Behera A. . Studies of hybrid ceria polypyrrole CPP-2 composite for effective defluoridation from potable water. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2024, 702: 135026

[27] Liu X, Rehman D, Shu Y. . Selective fluoride removal from groundwater using CNT-CeO₂ electrodes in capacitive deionization (CDI). Chemical Engineering Journal, 2024, 482: 149097

[28] Wang T, Gang H, Cao Y. . Hydrous CeO₂ polypyrrole nanocomposite as a stable and efficient adsorbent for defluoridation of acidic wastewater. Journal of Materials Science, 2023, 58(19): 7895–7914

[29] Jian S, Shi F, Hu R. . Electrospun magnetic La₂O₃–CeO₂–Fe₃O₄ composite nanofibers for removal of fluoride from aqueous solution. Composites Communications, 2022, 33: 101194

[30] Chen F, Lv F, Li H. . Evaluation of fluoride adsorption in solution by synthetic Al₂O₃/CeO₂: A fixed-bed column study. Water Environment Research, 2021, 93(11): 2559–2575

[31] Wang K, Lei H, Muhammad Y. . Controlled preparation of cerium oxide loaded slag-based geopolymer microspheres (CeO₂@ SGMs) for the adsorptive removal and solidification of F^– from acidic waste-water. Journal of Hazardous Materials, 2020, 400: 123199

[32] Wang F, Wang K, Muhammad Y. . Preparation of CeO₂@ SiO₂ microspheres by a non-sintering strategy for highly selective and continuous adsorption of fluoride ions from wastewater. ACS Sustainable Chemistry & Engineering, 2019, 7(17): 14716–14726

[33] Wilklow-Marnell M, Jones W D. Catalytic oxidation of carbon monoxide by α-alumina supported 3 nm cerium dioxide nanoparticles. Molecular Catalysis, 2017, 439: 9–14

[34] Cha X, He J, Fu Y. . Carbonate-mediated Mars-van Krevelen mechanism on Cu_xO/CeO₂ catalysts for boosting CO oxidation. Chemical Engineering Journal, 2024, 501: 157643

[35] Sun C, Sun J, Xiao G. . Mesoscale organization of nearly monodisperse flowerlike ceria microspheres. Journal of Physical Chemistry B, 2006, 110(27): 13445–13452

[36] Liao Z, Zhang S, Li K. . Hazard analysis of thermally abused lithium-ion batteries at different state of charges. Journal of Energy Storage, 2020, 27: 101065

[37] Andersson P, Blomqvist P, Lorén A. . Using Fourier transform infrared spectroscopy to determine toxic gases in fires with lithium-ion batteries. Fire and Materials, 2016, 40(8): 999–1015

[38] Sun J, Li J, Zhou T. . Toxicity, a serious concern of thermal runaway from commercial Li-ion battery. Nano Energy, 2016, 27: 313–319

[39] Vincent J L, Crozier P A. Atomic level fluxional behavior and activity of CeO₂-supported Pt catalysts for CO oxidation. Nature Communications, 2021, 12(1): 5789

[40] Rashid U S, Das T K, Sakthivel T S. . GO-CeO₂ nanohybrid for ultra-rapid fluoride removal from drinking water. Science of the Total Environment, 2021, 793: 148547

[41] Seal S, Jeyaranjan A, Neal C J. . Engineered defects in cerium oxides: tuning chemical reactivity for biomedical, environmental, & energy applications. Nanoscale, 2020, 12(13): 6879–6899

[42] Slater J C. Atomic radii in crystals. Journal of Chemical Physics, 1964, 41(10): 3199–3204

[43] Vento-Lujano E, González L A. Defect-induced modification of band structure by the insertion of Ce³⁺ and Ce⁴⁺ in SrTiO₃: A high-performance sunlight-driven photocatalyst. Applied Surface Science, 2021, 569: 151044

[44] Ahmad S, Gopalaiah K, Chandrudu S N. . Anion (fluoride)-doped ceria nanocrystals: Synthesis, characterization, and its catalytic application to oxidative coupling of benzylamines. Inorganic Chemistry, 2014, 53(4): 2030–2039

[45] Nair S, Bose R, Durani S. . An eco-friendly and low-cost methodology for fluoride adsorption using synthesized and characterized ceria-impregnated activated graphite (CIAG). Chemicke Zvesti, 2024, 78(6): 3883–3906

[46] Pan Y, Liu X, Zhang M. . The impact of redox annealing on intrinsic properties and fluoride adsorption performance of CeO₂ nanomaterials. Chemical Engineering Journal, 2023, 476: 146347

[47] Liu X, Jia S, Yang M. . Activation of subnanometric Pt on Cu-modified CeO₂ via redox-coupled atomic layer deposition for CO oxidation. Nature Communications, 2020, 11(1): 4240

[48] Hamaloğlu K Ö, Tosun R B, Ulu S. . Monodisperse-porous cerium oxide microspheres as a new support with appreciable catalytic activity for a composite catalyst in benzyl alcohol oxidation. New Journal of Chemistry, 2021, 45(4): 2019–2029

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