Graphite vs. lithium metal anodes: Safety of hybrid solid-liquid lithium batteries under short circuit and nail penetration

doi:10.19799/j.cnki.2095-4239.2025.0298

Abstract

Abstract:

Although lithium-ion batteries are widely adopted, their safety remains a critical bottleneck that limits further technological advancement. This study investigates how anode materials influence the thermal runaway pathways of ternary pouch cells by examining the safety responses of graphite and lithium metal anodes under nail penetration and external short-circuit conditions. By simultaneously monitoring key parameters, including temperature, voltage, current, and analyzing electrode interface morphology and contact status, this study demonstrates that anode properties fundamentally affect failure mechanisms during thermal events. In external short-circuit tests, the highly reactive lithium metal anode, together with powdery lithium deposits formed after cycling, exacerbates exothermic side reactions, resulting in significantly higher peak currents (148.7 A vs. 100.9 A) and maximum temperatures (273 ℃ vs. 104 ℃) than those observed with graphite anode, indicating a substantially greater risk of thermal runaway. Conversely, lithium metal anodes exhibit superior safety performance during nail penetration tests. Localized melting at the penetration site, along with subsequent physical detachment and rapid chemical passivation, leads to a sharp increase in contact resistance (>40 Ω), which effectively interrupting interrupts the internal short circuit and prevents thermal runaway. In contrast, the rigid structure of graphite anodes maintains the short-circuit pathway, causing rapid heat accumulation, with peak temperature rates exceeding 420 ℃/s. Overall, this study reveals the structure-property-failure relationship between anode materials and their associated thermal behaviors, providing valuable insights for the design of lithium batteries that combine high energy density with enhanced safety through targeted anode modification.

Key words: lithium-ion battery, lithium metal, nail penetration, short circuit, thermal runaway

CLC Number:

TM 911

Ronghan QIAO, Lin SANG, Zhongyang ZHANG, Xiayin YAO, Xingjiang LIU, Hailong YU. Graphite vs. lithium metal anodes: Safety of hybrid solid-liquid lithium batteries under short circuit and nail penetration[J]. Energy Storage Science and Technology, 2025, 14(10): 3657-3665.

Figures/Tables 12

Table 1

Fig. 1

Fig. 2

Fig. 3

Fig. 4

Fig. 5

Fig. 6

Fig. 7

Fig. 8

Fig. 9

Table 2

Fig. 10

References 25

[1]	中国汽车工业协会, 中国汽车工程研究院股份有限公司, 一汽解放集团股份有限公司. 中国商用汽车产业发展报告(2024)[M]. 北京: 社会科学文献出版社, 2024.
[2]	GOODENOUGH J B, KIM Y. Challenges for rechargeable Li batteries[J]. Chemistry of Materials, 2010, 22(3): 587-603. DOI: 10.1021/cm901452z.
[3]	王莉, 谢乐琼, 田光宇, 等. 锂离子电池安全事故: 安全性问题,还是可靠性问题[J]. 储能科学与技术, 2021, 10(1): 1-6. DOI: 10.19799/j.cnki.2095-4239.2020.0345.
	WANG L, XIE L Q, TIAN G Y, et al. Safety accidents of Li-ion batteries: Reliability issues or safety issues[J]. Energy Storage Science and Technology, 2021, 10(1): 1-6. DOI: 10.19799/j.cnki. 2095-4239.2020.0345.
[4]	FENG X N, OUYANG M G, LIU X, et al. Thermal runaway mechanism of lithium ion battery for electric vehicles: A review[J]. Energy Storage Materials, 2018, 10: 246-267. DOI: 10.1016/j.ensm.2017.05.013.
[5]	靳欣, 张建茹, 王其钰, 等. 混合固液锂离子电池的热失控行为研究[J]. 储能科学与技术, 2024, 13(1): 48-56. DOI: 10.19799/j.cnki.2095-4239.2023.0846.
	JIN X, ZHANG J R, WANG Q Y, et al. Study on thermal runaway of hybrid solid-liquid batteries[J]. Energy Storage Science and Technology, 2024, 13(1): 48-56. DOI: 10.19799/j.cnki.2095-4239.2023.0846.
[6]	OUYANG D X, CHEN M Y, HUANG Q, et al. A review on the thermal hazards of the lithium-ion battery and the corresponding countermeasures[J]. Applied Sciences, 2019, 9(12): 2483. DOI: 10.3390/app9122483.
[7]	SPOTNITZ R, FRANKLIN J. Abuse behavior of high-power, lithium-ion cells[J]. Journal of Power Sources, 2003, 113(1): 81-100. DOI: 10.1016/S0378-7753(02)00488-3.
[8]	田君, 田崔钧, 王一拓, 等. 锂离子电池安全性测试与评价方法分析[J]. 储能科学与技术, 2018, 7(6): 1128-1134. DOI: 10.12028/j.issn.2095-4239.2018.0154.
	TIAN J, TIAN C J, WANG Y T, et al. Safety test and evaluation method of lithium ion battery[J]. Energy Storage Science and Technology, 2018, 7(6): 1128-1134. DOI: 10.12028/j.issn.2095-4239.2018.0154.
[9]	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. 电动汽车用动力蓄电池安全要求及试验方法: GB/T 31485—2015[S]. 北京: 中国标准出版社, 2015.
[10]	CHENG X B, ZHANG R, ZHAO C Z, et al. Toward safe lithium metal anode in rechargeable batteries: A review[J]. Chemical Reviews, 2017, 117(15): 10403-10473. DOI: 10.1021/acs.chemrev. 7b00115.
[11]	ZHANG H, YANG Y, REN D S, et al. Graphite as anode materials: Fundamental mechanism, recent progress and advances[J]. Energy Storage Materials, 2021, 36: 147-170. DOI: 10.1016/j.ensm.2020.12.027.
[12]	李启全. 锂电池安全测试分析[J]. 电池工业, 2017, 21(2): 4-6. DOI: 10.3969/j.issn.1008-7923.2017.02.002.
	LI Q Q. Safety test of lithium battery[J]. Chinese Battery Industry, 2017, 21(2): 4-6. DOI: 10.3969/j.issn.1008-7923.2017.02.002.
[13]	LIU B, ZHANG J G, XU W. Advancing lithium metal batteries[J]. Joule, 2018, 2(5): 833-845. DOI: 10.1016/j.joule.2018.03.008.
[14]	GAO M D, LI H, XU L, et al. Lithium metal batteries for high energy density: Fundamental electrochemistry and challenges[J]. Journal of Energy Chemistry, 2021, 59: 666-687. DOI: 10.1016/j.jechem.2020.11.034.
[15]	ZHANG S S. A review on electrolyte additives for lithium-ion batteries[J]. Journal of Power Sources, 2006, 162(2): 1379-1394. DOI: 10.1016/j.jpowsour.2006.07.074.
[16]	YUE X Y, MA C, BAO J, et al. Failure mechanisms of lithium metal anode and their advanced characterization technologies[J]. Acta Physico Chimica Sinica, 2020, 37(2): DOI: 10.3866/pku.whxb202005012.
[17]	LAMB J, ORENDORFF C J, ROTH E P, et al. Studies on the thermal breakdown of common Li-ion battery electrolyte components[J]. Journal of the Electrochemical Society, 2015, 162(10): A2131-A2135. DOI: 10.1149/2.0651510jes.
[18]	张世超, 沈泽宇, 陆盈盈. 金属锂电池的热失控与安全性研究进展[J]. 物理化学学报, 2021, 37(1): 61-78. DOI: 10.3866/PKU.WHXB 202008065.
	ZHANG S C, SHEN Z Y, LU Y Y. Research progress of thermal runaway and safety for lithium metal batteries[J]. Acta Physico-Chimica Sinica, 2021, 37(1): 61-78. DOI: 10.3866/PKU.WHXB 202008065.
[19]	CAI T, PANNALA S, STEFANOPOULOU A G, et al. Battery internal short detection methodology using cell swelling measurements[C]//2020 American Control Conference (ACC). July 1-3, 2020, Denver, CO, USA. IEEE, 2020: 1143-1148.
[20]	JIA L Z, WANG D, YIN T, et al. Experimental study on thermal-induced runaway in high nickel ternary batteries[J]. ACS Omega, 2022, 7(17): 14562-14570. DOI: 10.1021/acsomega.1c06495.
[21]	ZHANG Y Y, HEIM F M, SONG N N, et al. New insights into mossy Li induced anode degradation and its formation mechanism in Li-S batteries[J]. Acs Energy Letters, 2017, 2(12): 2696-2705. DOI: 10.1021/acsenergylett.7b00886.
[22]	梁宏毅, 王媛, 甘友毅, 等. 三元动力锂离子电池内短路热失控残骸的特征[J]. 电池, 2024, 54(4): 487-491.DOI:10.19535/j.1001-1579.2024.04.010.
	LIANG H Y, WANG Y, GAN Y Y,et al. Characteristics of residue of ternary Li-ion traction battery induced by internal short-circuit[J]. Dianchi(Battery Bimonthly), 2024, 54(4): 487-491. DOI:10.19535/j.1001-1579.2024.04.010.
[23]	HILDEBRAND J H, LAMOREAUX R H. Viscosity of liquid metals: An interpretation[J]. Proceedings of the National Academy of Sciences of the United States of America, 1976, 73(4): 988-989. DOI: 10.1073/pnas.73.4.988.
[24]	LI Z, HUANG J, YANN LIAW B, et al. A review of lithium deposition in lithium-ion and lithium metal secondary batteries[J]. Journal of Power Sources, 2014, 254: 168-182. DOI: 10.1016/j.jpowsour.2013.12.099.
[25]	BAI W, XIAO L, LONG T, et al. Fire-retardant and thermally conductive polyacrylonitrile-based separators enabling the safety of lithium-ion batteries[J]. Journal of Colloid and Interface Science, 2025, 684: 377-387. DOI: 10.1016/j.jcis.2024.12.229.

样品	正极	负极	电压/V	容量/Ah	内阻/mΩ	测试方法
石墨-短路	NCM811	石墨	2.8~4.2	3.6	7.87	短路测试
锂金属-短路	NCM811	锂金属	2.8~4.3	3.6	12.35	短路测试
石墨-针刺	NCM811	石墨	2.8~4.2	3.6	11.38	针刺测试
锂金属-针刺	NCM811	锂金属	2.8~4.3	3.6	15.14	针刺测试

项目	正极-负极	正极-钢针	钢针-负极
石墨-针刺电池电压	0	0	0
石墨-针刺电池电阻	19.78 Ω	24.52 Ω	4.33 Ω
金属锂-针刺电池电压	4.19 V	4.08 V	0.11 V
金属锂-针刺电池电阻	0.07 Ω	43.57 Ω	42.47 Ω