Experimental study of thermal runaway characteristics of large-capacity sodium-ion batteries

doi:10.19799/j.cnki.2095-4239.2024.1044

Abstract

Abstract:

Sodium-ion batteries (SIBs) hold significant promise for electrochemical energy storage owing to their abundant raw materials and cost-effectiveness. However, as SIBs become more widely adopted in energy storage systems, safety concerns are becoming more pronounced, attracting significant research attention globally. This study systematically investigates the thermal runaway (TR) behavior of SIBs under overheating conditions, with a comparative focus on the effects of different cathode materials on battery safety. The findings reveal that the NaNi_1/3Fe_1/3Mn_1/3O₂ batteries exhibit a lower TR trigger temperature, shorter trigger time, and higher surface temperatures compared to Na₃V₂(PO₄)₃ batteries, indicating a higher risk of TR. Constant-capacity tank tests further reveal that SIBs produce substantial gas during TR. Specifically, with NaNi_1/3Fe_1/3Mn_1/3O₂ and Na₃V₂(PO₄)₃batteries produce 14.58 and 13.16 mol of gas, respectively, corresponding to lower explosion limits of 7.5% and 8.0%. These results provide crucial theoretical insights and technical support for improving the safety design and risk management strategies of sodium-based energy storage systems.

Key words: sodium-ion battery, thermal runaway behavior, gas production behavior, explosion hazard

CLC Number:

TM 911

Yongqi LI, Zhiyuan LI, Youwei WEN, Chengdong WANG, Qiangling DUAN, Qingsong WANG. Experimental study of thermal runaway characteristics of large-capacity sodium-ion batteries[J]. Energy Storage Science and Technology, 2025, 14(4): 1657-1667.

Figures/Tables 13

Table 1

Fig. 1

Fig. 2

Fig. 3

Fig. 4

Table 2

Fig. 5

Fig. 6

Fig. 7

Fig. 8

Fig. 9

Table 3

Fig. 10

References 29

1	WANG Y, FENG X N, GUO D X, et al. Temperature excavation to boost machine learning battery thermochemical predictions[J]. Joule, 2024, 8(9): 2639-2651. DOI: 10.1016/j.joule.2024.07.002.
2	LU Z X, WANG J, FENG W L, et al. Zinc single-atom-regulated hard carbons for high-rate and low-temperature sodium-ion batteries[J]. Advanced Materials, 2023, 35(26): 2211461. DOI: 10.1002/adma.202211461.
3	WANG L L, ZHU J C, LI N, et al. Superior electrochemical performance of alkali metal anodes enabled by milder Lewis acidity[J]. Energy & Environmental Science, 2024, 17(10): 3470-3481. DOI: 10.1039/D4EE00900B.
4	TARASCON J M. Na-ion versus Li-ion batteries: Complementarity rather than competitiveness[J]. Joule, 2020, 4(8): 1616-1620. DOI: 10.1016/j.joule.2020.06.003.
5	ZHU K J, SUN Z Q, LI Z P, et al. Aqueous sodium ion hybrid batteries with ultra-long cycle life at -50 ℃[J]. Energy Storage Materials, 2022, 53: 523-531. DOI: 10.1016/j.ensm.2022.09.019.
6	PARK S, WANG Z, CHOUDHARY K, et al. Obtaining V₂(PO₄)₃ by sodium extraction from single-phase NaxV₂(PO₄)₃ (1 < x < 3) positive electrode materials[J]. Nature Materials, 2024[2024-11-04]. https://www.nature.com/articles/s41563-024-02023-7. DOI: 10.1038/s41563-024-02023-7.
7	REN D S, LIU X, FENG X N, et al. Model-based thermal runaway prediction of lithium-ion batteries from kinetics analysis of cell components[J]. Applied Energy, 2018, 228: 633-644. DOI: 10. 1016/j.apenergy.2018.06.126.
8	ZHANG Y, SONG L F, TIAN J M, et al. Modeling the propagation of internal thermal runaway in lithium-ion battery[J]. Applied Energy, 2024, 362: 123004. DOI: 10.1016/j.apenergy.2024. 123004.
9	WANG G Q, PING P, PENG R Q, et al. A semi reduced-order model for multi-scale simulation of fire propagation of lithium-ion batteries in energy storage system[J]. Renewable and Sustainable Energy Reviews, 2023, 186: 113672. DOI: 10.1016/j.rser.2023.113672.
10	WANG G Q, KONG D P, PING P, et al. Modeling venting behavior of lithium-ion batteries during thermal runaway propagation by coupling CFD and thermal resistance network[J]. Applied Energy, 2023, 334: 120660. DOI: 10.1016/j.apenergy. 2023.120660.
11	JIA Z Z, MIN Y Y, QIN P, et al. Effect of safety valve types on the gas venting behavior and thermal runaway hazard severity of large-format prismatic lithium iron phosphate batteries[J]. Journal of Energy Chemistry, 2024, 89: 195-207. DOI: 10.1016/j.jechem. 2023.09.052.
12	JIA Z Z, SONG L F, MEI W X, et al. The preload force effect on the thermal runaway and venting behaviors of large-format prismatic LiFePO₄ batteries[J]. Applied Energy, 2022, 327: 120100. DOI: 10.1016/j.apenergy.2022.120100.
13	MEI W X, LIU Z, WANG C D, et al. operando monitoring of thermal runaway in commercial lithium-ion cells via advanced lab-on-fiber technologies[J]. Nature Communications, 2023, 14(1): 5251. DOI: 10.1038/s41467-023-40995-3.
14	WANG H B, XU H, ZHANG Z L, et al. Fire and explosion characteristics of vent gas from lithium-ion batteries after thermal runaway: A comparative study[J]. eTransportation, 2022, 13: 100190. DOI: 10.1016/j.etran.2022.100190.
15	PENG Y, YANG L Z, JU X Y, et al. A comprehensive investigation on the thermal and toxic hazards of large format lithium-ion batteries with LiFePO₄ cathode[J]. Journal of Hazardous Materials, 2020, 381: 120916. DOI: 10.1016/j.jhazmat.2019. 120916.
16	LI J Y, TONG B, GAO P, et al. A novel method to determine the multi-phase ejection parameters of high-density battery thermal runaway[J]. Journal of Power Sources, 2024, 592: 233905. DOI: 10.1016/j.jpowsour.2023.233905.
17	HWANG S, LEE Y, JO E, et al. Investigation of thermal stability of P2-NaxCoO₂ cathode materials for sodium ion batteries using real-time electron microscopy[J]. ACS Applied Materials & Interfaces, 2017, 9(22): 18883-18888. DOI: 10.1021/acsami.7b04478.
18	HEUBNER C, SCHNEIDER M, MICHAELIS A. Heat generation rates of NaFePO₄ electrodes for sodium-ion batteries and LiFePO₄ electrodes for lithium-ion batteries: A comparative study[J]. Journal of Solid State Electrochemistry, 2018, 22(4): 1099-1108. DOI: 10.1007/s10008-017-3828-4.
19	ROBINSON J B, FINEGAN D P, HEENAN T M M, et al. Microstructural analysis of the effects of thermal runaway on Li-ion and Na-ion battery electrodes[J]. Journal of Electrochemical Energy Conversion and Storage, 2018, 15(1): 011010. DOI: 10. 1115/1.4038518.
20	BORDES A, MARLAIR G, ZANTMAN A, et al. Safety evaluation of a sodium-ion cell: Assessment of vent gas emissions under thermal runaway[J]. ACS Energy Letters, 2022, 7(10): 3386-3391. DOI: 10.1021/acsenergylett.2c01667.
21	YUE Y B, JIA Z Z, LI Y Q, et al. Thermal runaway hazards comparison between sodium-ion and lithium-ion batteries using accelerating rate calorimetry[J]. Process Safety and Environmental Protection, 2024, 189: 61-70. DOI: 10.1016/j.psep.2024.06.032.
22	YANG C, XIN S, MAI L Q, et al. Materials design for high-safety sodium-ion battery[J]. Advanced Energy Materials, 2021, 11(2): 2000974. DOI: 10.1002/aenm.202000974.
23	HUANG Z H, SHEN T, JIN K Q, et al. Heating power effect on the thermal runaway characteristics of large-format lithium ion battery with Li(Ni_1/3Co_1/3Mn_1/3)O₂ as cathode[J]. Energy, 2022, 239: 121885. DOI: 10.1016/j.energy.2021.121885.
24	HUANG Z H, YU Y, DUAN Q L, et al. Heating position effect on internal thermal runaway propagation in large-format lithium iron phosphate battery[J]. Applied Energy, 2022, 325: 119778. DOI: 10.1016/j.apenergy.2022.119778.
25	LI H, DUAN Q L, ZHAO C P, et al. Experimental investigation on the thermal runaway and its propagation in the large format battery module with Li(Ni_1/3Co_1/3Mn_1/3)O₂ as cathode[J]. Journal of Hazardous Materials, 2019, 375: 241-254. DOI: 10.1016/j.jhazmat.2019.03.116.
26	ZHOU Z Z, ZHOU X D, PENG Y, et al. Quantitative study on the thermal failure features of lithium iron phosphate batteries under varied heating powers[J]. Applied Thermal Engineering, 2021, 185: 116346. DOI: 10.1016/j.applthermaleng.2020.116346.
27	WEI G, HUANG R J, ZHANG G X, et al. A comprehensive insight into the thermal runaway issues in the view of lithium-ion battery intrinsic safety performance and venting gas explosion hazards[J]. Applied Energy, 2023, 349: 121651. DOI: 10.1016/j.apenergy. 2023.121651.
28	MEI W X, CHENG Z X, WANG L B, et al. Thermal hazard comparison and assessment of Li-ion battery and Na-ion battery[J]. Journal of Energy Chemistry, 2025, 102: 18-26. DOI: 10.1016/j.jechem.2024.10.036.
29	LI Z Y, CHENG Z X, YU Y, et al. Thermal runaway comparison and assessment between sodium-ion and lithium-ion batteries[J]. Process Safety and Environmental Protection, 2025, 193: 842-855. DOI: 10.1016/j.psep.2024.11.118.

参数	单位	样品电池1	样品电池2
标称容量	Ah	220	230
电池尺寸	mm	173.0×72.0×204.0	174.2×72.0×204.2
质量	g	4900±500	5100±200
标称电压	V	3.1	2.9
充放电电压	V	2.0~3.85	2.0~3.85
荷电状态	—	100%	100%
正极材料	—	NaNi_1/3Fe_1/3Mn_1/3O₂	Na₃V₂(PO₄)₃
负极材料	—	硬碳	硬碳

电池类型	T_onset/℃	t_onset/s	T_max/℃	Δt_TRP/s	v_TRP/(mm/s)
NaNi_1/3Fe_1/3Mn_1/3O₂	266.3	321	1082.9	88	0.818
Na₃V₂(PO₄)₃	284.4	398	996.0	105	0.686

电池类型	t_onset/s	M_Loss/g	Vgas/L	T_gas/℃	LEL/%
NaNi_1/3Fe_1/3Mn_1/3O₂	321	1240.2	326.6	263.8	7.5
Na₃V₂(PO₄)₃	398	1406.3	294.8	173.9	8.0

[1]	Youwei WEN, Anqi TENG, Yongqi LI, Jiamin TIAN, Kangjie DING, Qiangling DUAN, Qingsong WANG. Electrical performance and heat production behavior of sodium-ion batteries at different discharge rate [J]. Energy Storage Science and Technology, 2025, 14(4): 1687-1697.
[2]	Lan WU, Jie YANG, Lei GENG, Run HU, Shanglong PENG. Residual alkali converted sodium compensation cladding on the surface of sodium ion battery cathode [J]. Energy Storage Science and Technology, 2025, 14(1): 21-29.
[3]	Chengfan JIANG, Jun HUANG, Haibo XIE. Improving the initial coulombic efficiency of hard carbon materials for sodium-ion batteries [J]. Energy Storage Science and Technology, 2024, 13(3): 825-840.
[4]	Ke LI, Yifan HAO, Zhenhua FANG, Jing WANG, Songtong ZHANG, Xiayu ZHU, Jingyi QIU, Hai MING. Development and military application analysis of high-power chemical power supply system [J]. Energy Storage Science and Technology, 2024, 13(2): 436-461.
[5]	Cuihong ZENG, Xiujuan CHEN, Man LI, Wenji YIN, Jiming PENG, Sijiang HU, Youguo HUANG, Hongqiang WANG, Qingyu LI. Investigation of W-doped P2-Na_0.6Li_0.27Mn_0.73O₂ cathode materials for sodium-ion batteries [J]. Energy Storage Science and Technology, 2024, 13(11): 3731-3741.
[6]	Ding ZHANG, Zixian YE, Zhenming LIU, Qun YI, Lijuan SHI, Huijuan GUO, Yi HUANG, Li WANG, Xiangming HE. Research progress of black phosphorus-based anode materials for sodium-ion batteries [J]. Energy Storage Science and Technology, 2023, 12(8): 2482-2490.
[7]	Man CHEN, Zhixiang CHENG, Chunpeng ZHAO, Peng PENG, Qikai LEI, Kaiqiang JIN, Qingsong WANG. Numerical simulation study on explosion hazards of lithium-ion battery energy storage containers [J]. Energy Storage Science and Technology, 2023, 12(8): 2594-2605.
[8]	Junpeng GUO, Qi SUN, Yuefang CHEN, Yuwen ZHAO, Huan YANG, Zhijia ZHANG. Preparation of three-dimensional multistage iron oxide/carbon nanofiber integrated electrode and sodium storage performance [J]. Energy Storage Science and Technology, 2023, 12(5): 1469-1479.
[9]	Xue YUAN, Hongji LI, Wenhui BAI, Zhengxi LI, Libin YANG, Kai WANG, Zhe CHEN. Application of biomass-derived carbon-based anode materials in sodium ion battery [J]. Energy Storage Science and Technology, 2023, 12(3): 721-742.
[10]	Xiongwen XU, Yang NIE, Jian TU, Zheng XU, Jian XIE, Xinbing ZHAO. Abuse performance of pouch-type Na-ion batteries based on Prussian blue cathode [J]. Energy Storage Science and Technology, 2022, 11(7): 2030-2039.
[11]	Haiyan HU, Shulei CHOU, Yao XIAO. Layered oxide cathode materials based on molecular orbital hybridization for high voltage sodium-ion batteries [J]. Energy Storage Science and Technology, 2022, 11(4): 1093-1102.
[12]	Zhiqiang ZHAO, Hengjun LIU, Xixiang XU, Yuanyuan PAN, Qinghao LI, Hongsen LI, Han HU, Qiang LI. Magnetometry technique in energy storage science [J]. Energy Storage Science and Technology, 2022, 11(3): 818-833.
[13]	Fei LIU, Peiwen ZHAO, Jingxiang ZHAO, Xianwei SUN, Miaomiao LI, Jinghao WANG, Yanxin YIN, Zuoqiang DAI, Lili ZHENG. Research progress of hard carbon anode materials for sodium ion batteries [J]. Energy Storage Science and Technology, 2022, 11(11): 3497-3509.
[14]	Zhihui GUO, Xiaodan CUI, Linshuang ZHAO, Jiawei CHEN. Fire and gas explosion hazards of high-nickel lithium-ion battery [J]. Energy Storage Science and Technology, 2022, 11(1): 193-200.
[15]	Yifeng FENG, Jiani SHEN, Haiying CHE, Zifeng MA, Yijun HE, Wen TAN, Qingheng YANG. State of health prediction for sodium-ion batteries [J]. Energy Storage Science and Technology, 2021, 10(4): 1407-1415.