Design and development of high-stability lithium metal anodes

doi:10.19799/j.cnki.2095-4239.2025.0977

Abstract

Abstract: Although lithium metal anodes exhibit an exceptionally high specific capacity and are ideal candidates for high-energy-density rechargeable lithium batteries, safety concerns have severely hindered their practical application. With a heat release significantly surpassing that of other battery components, improving thermal-safety performance of lithium metal anodes is the key to determining the overall safety of lithium-metal batteries. Accordingly, this work develops an ultrathin (20 μm) Li-Zn (Li_0.7Zn_0.3) alloy anode that is suitable for large-scale production. The as-prepared Li_0.7Zn_0.3 exhibits exceptional stability and superior safety. This research reveals that this newly designed lithium alloy material remains stable after immersion in organic solvents for 30 days and does not ignite upon contact with water, resolving the issue of pure lithium (Li) catching fire in the presence of water. After storage at 60 ℃ for 30 days, the Li_0.7Zn_0.3||Cu half-cell delivers 98.5% of the delithiation capacity of a fresh anode, indicating that interfacial side reactions are effectively suppressed. Differential scanning calorimetry (DSC) tests further demonstrates that this alloy anode exhibits superior thermal stability relative to pure Li after 30 cycles at 100% SOC, which is expected to significantly enhance battery safety. Adiabatic rate calorimetry (ARC) tests on pouch cells shows that replacing pure Li with alloy raises the thermal runaway trigger temperature (T₂) from 177.8 ℃ to 216.5 ℃. Furthermore, the maximum temperatures (T₃) during thermal runaway are reduced from 1940.0 ℃ to 1191.5 ℃. In particular, a high-capacity (53.60 Ah) pouch cell based on this new alloy anode delivers a high energy density of 509.25 Wh/kg and maintains stable cycling for 120 cycles. Collectively, this work introduces a low-cost, easily-prepared Li0.7Zn0.3 alloy with inherently high safety, which markedly elevates the safety profile of lithium metal batteries and furnishes critical technical groundwork for their industrial deployment.

Key words: lithium metal battery, 500 Wh/kg, lithium alloy, high safety, thermal runaway

CLC Number:

CUI Yanming, QIAN Yao, ZHAO Yanchun, HUANG Yuanqiao, CHEN Shiwei, LIN Jiu. Design and development of high-stability lithium metal anodes[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2025.0977.

References

[1]LIU J, BAO Z Z, CUI Y, et al. Pathways for practical high-energy long-cycling lithium metal batteries [J]. Nature Energy, 2019, 4: 180–186. DOI:10.1038/s41560-019-0338-x. [百度学术]
[2]QING P, WU Z B, WANG A B, et al. Highly Reversible Lithium Metal Anode Enabled by 3D Lithiophilic-Lithiophobic Dual-Skeletons[J]. Advanced Materials, 2023, 35(15): 2211203. DOI: 10.1002/adma.202211203. [百度学术]
[3]QING P, HUANG S Z, NAREN T Y, et al. Interpenetrating LiB/Li3BN2 phases enabling stable composite lithium metal anode[J].Science Bulletin, 2024, 69(18): 2842-2852. DOI: 10.1016/j. scib.2024.07.021. [百度学术]
[4]ALBERTUS P, BABINEC S, LITZELMAN S, et al. Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries[J]. Nature Energy, 2018, 3:16-21. DOI:10.1038/s41560-017-0047-2. [百度学术]
[5]LI S, JIANG M, XIE Y, et al. Developing high‐performance lithium metal anode in liquid electrolytes: challenges and progress[J]. Advanced Materials, 2018, 30: 1706375. DOI: 10.1002/adma.201706375. [百度学术]
[6]ZHANG C, FAN H M, CHEN X L, et al. Non-stick Li-alloy leaf for long-lasting secondary batteries[J]. Energy & Environmental Science, 2022,15: 5251-5260. DOI:10.1039/d2ee02135h. [百度学术]
[7]崔言明, 林久, 马贺礼, 等. 一种飞行器用高安全、长寿命的锂金属电池模组: 202410905593.X [P]. 2024-10-11. [百度学术] CUI Y M, LIN J, MA H L, et al. A high-safety, long-life lithium metal battery module for aircraft: 202410905593.X [P]. 2024-10-11. [百度学术]
[8]许晓雄, 崔言明, 秦晨阳, 等. 一种锂金属电池负极材料及其制备方法和锂金属电池:202210595281.1 [P]. 2022-05-28. [百度学术] XU X X, CUI Y M, QIN C Y, et al. A lithium metal anode material, its preparation method, and a lithium metal battery:202210595281.1 [P]. 2022-05-28. [百度学术]
[9]李良彬, 彭良平, 周金根, 等. 一种超薄锂带制备的挤压模具组合装置: 202322860850.6 [P]. 2023-10-24. [百度学术]
LI L B, PENG L P, ZHOU J Y, et al. An extrusion die assembly for ultra-thin lithium strip production: 202322860850.6 [P]. 2023-10-24. [百度学术]
[10]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. 锂带:GB/T 20930—2015 [S]. 北京:中国标准出版社, 2015. [百度学术] General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China, Standardization Administration of the People's Republic of China. Lithium strip: GB/T 20930—2015 [S]. Beijing:Standards Press of China, 2015. [百度学术]
[11]PUTHUSSERI D, PARMANANDA M, MUKHERJEE P P, et al. Probing the thermal safety of Li metal batteries[J]. Journal of The Electrochemical Society, 2020, 167: 120513. DOI: 10.1149/1945-7111/ababd2. [百度学术]
[12]ZHANG K, WU F, WANG X, et al. 8.5 µm-thick flexible-rigid hybrid solid–electrolyte/lithium integration for air-stable and interface-compatible all-solid-state lithium metal batteries[J]. Advanced Energy Materials, 2022, 12: 2200368. DOI: 10.1002/aenm.202200368. [百度学术]
[13]LI Y Q, LIU Q A, WU Y S, et al. Unraveling the reaction mystery of Li and Na with dry air[J]. Journal of the American Chemical Society, 2023, 145: 10576. DOI: 10.1021/jacs.2c13589. [百度学术]
[14]SCHIEMANN M, BERGTHORSON J, FISCHER P, et al. A review on lithium combustion[J]. Applied Energy, 2016, 162: 948. DOI: 10.1016/j.apenergy.2015.10.172. [百度学术]
[15]WU Y, ZENG Z, ZHANG H, et al. Constructing thermo-responsive polysiloxane shields via lithium initiation to inhibit thermal runaway of lithium metal batteries[J]. Energy Storage Materials, 2024, 70:103499. DOI: 10.1016/j.ensm.2024.103499. [百度学术]
[16]JIANG F N, CHENG X B, YANG S J, et al. Thermoresponsive electrolytes for safe lithium‐metal batteries[J]. Advanced Materials 2023, 35, 2209114. DOI: 10.1002/adma.202209114. [百度学术]
[17]CHENG X B, YANG S J, LIU Z C, et al. Electrochemically and thermally stable inorganics-rich solid electrolyte interphase for robust lithium metal batteries[J]. Advanced Materials, 2024, 36(1): 2307370. DOI:10.1002/adma.202307370. [百度学术]
[18]ZENG X Y, CHEN Y, NIE H, et al. Advanced poly (ether ether ketone) separator for lithium metal battery[J]. Small, 2025, 21(13): 2411626. DOI: 10.1002/smll.202411626. [百度学术]
[19]HAN L F, ZHANG M D, CAO Y K, et al. High fire-safety, thinning lithium metal anode for high-energy-density lithium metal batteries[J]. Advanced Functional Materials, 2025: 2504427. DOI: 10.1002/adfm.202504427. [百度学术]
[20]WU W Y, LUO W, HUANG Y H. Less is more: a perspective on thinning lithium metal towards high-energy-density rechargeable lithium batteries[J]. Chemical Society Review, 2023,52, 2553-2572 DOI: 10.1039/d2cs00606e. [百度学术]
[21]BURTON M, NARAYANAN S, JAGGER B, et al. Techno-economic assessment of thin lithium metal anodes for solid-state batteries[J]. Nature Energy, 2025, 10: 135–147. DOI:10.1038/s41560-024-01676-7. [百度学术]
[22]CHEN Q L, LI H, MEYERSON M L, et al. Li-Zn overlayer to facilitate uniform lithium deposition for lithium metal batteries[J]. ACS Applied Materials & Interfaces, 2021, 13: 9985-9993. DOI:10.1021/acsami.0c21195. [百度学术]
[23]OUYANG Y, CUI C, GUO Y P, et al. In-situ formed LiZn alloy skeleton for stable lithium anodes[J]. ACS Applied Materials & Interfaces, 2020, 12(23): 25818–25825. DOI: 10.1021/acsami.0c04092. [百度学术]
[24]ZHOU M Y, LIAO Y Q, LI L H, et al. Unraveling the heterogeneity of solid electrolyte interphase kinetically affecting lithium electrodeposition on lithium metal anode[J]. Journal of Energy Chemistry, 2023,85:181-190. DOI: 10.1016/j.jechem.2023.06.008. [百度学术]
[25]LI J R, SU H, LIU Y, et al. Li alloys in all solid-state lithium batteries: a review of fundamentals and applications[J]. Electrochemical Energy Reviews, 2024, 7:18. DOI: 10.1007/s41918-024-00221-0. [百度学术]
[26]LIN L, LIU F, YAN X L, et al. Dendrite-Free Reverse Lithium Deposition Induced by Ion Rectification Layer toward Superior Lithium Metal Batteries[J]. Advanced Functional Materials, 2021,31(40): 2104081.DOI: 10.1002/adfm.202104081. [百度学术]
[27]Li X Y, ZHU R J, JIANG H J, et al. Thickness-controllable Li–Zn composite anode for high-energy and low-N/P ratio lithium metal batteries[J]. Journal of Materials Chemistry A, 2022,10, 11246-11253. DOI: 10.1039/d2ta02162e. [百度学术]
[28]WANG Z H, SONG Z C, LIU Y C, et al. Stabilize Li metal anode through constructing LiZn alloy/polymer hybrid protective layer towards uniform Li deposition[J]. Physical Chemistry Chemical Physics, DOI: 10.1039/d2cp04787j. [百度学术]
[29]FENG X N, REN D S, HE X M, et al. Mitigating thermal runaway of lithium-Ion batteries[J]. Joule, 2020, 4: 743-770.DOI: 10.1016/j.joule.2020.02.010. [百度学术]
[30]FENG X N, REN D S, OUYANG M G. Safety of lithium battery materials chemistry[J]. Journal of Materials Chemistry A, 2023,11: 25236-25246. DOI: 10.1039/d3ta04182d. [百度学术]
[31]XU X Q, CHENG X B, JIANG F N, et al. Dendrite-accelerated thermal runaway mechanisms of lithium metal pouch batteries[J]. SusMat, 2022, 2: 435–444. DOI: 10.1002/sus2.74. [百度学术]
[32]WANG S L, ZHANG C Y, CHEN D P, et al. Explosion characteristics of two-phase ejecta from large-capacity lithium iron phosphate batteries[J]. eTransportation, 2024, 22: 100377. DOI: 10.1016/j.etran.2024.100377. [百度学术]
[33]ZHAO W H, MENG C, ZHAO Y R, et al. Research on aging-thermal characteristics coupling and aging thermal management analysis of large-capacity LiFePO4 battery. Journal of Energy Storage, 2025, 114:115675. DOI: 10.1016/j.est.2025.115675. [百度学术]