基于锂负极的液态金属电池研究进展

doi:10.19799/j.cnki.2095-4239.2023.0613

摘要/Abstract

摘要：

液态金属电池由于具有低成本、易于组装和扩容等优点，且在充放电过程中能够有效地避免枝晶生长和电极结构变形等问题，在规模化电网储能领域具有显著优势。本文系统地综述了液体金属电池的工作原理、优缺点、电池材料(包括电极和电解质)的选取原则以及近期液态金属电池电极材料的研究进展，着重介绍了Li‖Te体系、Li‖Bi体系、Li‖Sb体系、Li‖Sb-X(X=Pb，Sn)体系以及Li‖Bi-X(X=Sn，Pb)体系等以金属锂为负极的液态金属电池关键材料体系，重点分析了上述材料体系的电化学储能特性、安全性、循环稳定性以及性能提升策略，并对比分析了上述材料体系在大规模储能应用时存在的优势与不足。此外，综述了Li基液态金属电池在熔盐电解质、高温密封及腐蚀防护、电池热管理等方面存在的问题以及面临的技术难题。最后，展望了液态金属电池正、负极材料的主要发展方向。综合分析表明，基于Li负极的液态金属电池具有低熔点、低成本、高库仑效率以及高放电电压等优点。

关键词: 锂负极, 液态金属电池, 电化学储能, 关键材料

Abstract:

Liquid metal batteries have significant advantages in the field of large-scale power grid energy storage due to their low cost, easy assembly and expansion, and the ability to effectively avoid dendritic growth and electrode structure deformation during the charging and discharging processes. This article provides a systematic overview of the working principle, advantages and disadvantages, selection principles of battery materials (including electrodes and electrolytes), and the recent research progress on the electrode materials for liquid metal batteries, which focuses on introducing key material systems for liquid metal batteries using lithium as the negative electrode, such as the Li‖Te system, Li‖Bi system, Li‖Sb system, Li‖Sb-X (X=Pb, Sn) system, and Li‖Bi X (X=Sn, Pb) system. The electrochemical energy storage properties, safety, cycling stability, and performance improvement strategies of the above material systems were primarily analyzed, and the advantages and disadvantages of the above material systems in large-scale energy storage applications were evaluated and compared. Moreover, the problems and technical challenges faced by Li-based liquid metal batteries in molten salt electrolytes, high-temperature sealing and corrosion protection, and thermal management of batteries were reviewed. Finally, the main development directions of positive and negative electrode materials for liquid metal batteries were prospected. Comprehensive analysis shows that liquid metal batteries based on Li negative electrodes offer several advantages, such as low melting point, low cost, high Coulombic efficiency, and high discharge voltage.

Key words: lithium negative electrode, liquid metal batteries, electrochemical energy storage, key material

中图分类号:

TM 911

曾坤, 郑晓妍, 龚慧玲, 邹博, 陈凯, 晏忠钠. 基于锂负极的液态金属电池研究进展[J]. 储能科学与技术, 2024, 13(1): 299-310.

Kun ZENG, Xiaoyan ZHENG, Huiling GONG, Bo ZOU, Kai CHEN, Zhongna YAN. Research progress in liquid metal batteries based on lithium negative electrodes[J]. Energy Storage Science and Technology, 2024, 13(1): 299-310.

图/表 8

图1

图2

图3

表1

图4

图5

图6

图7

参考文献 64

1	黄雨涵, 丁涛, 李雨婷, 等. 碳中和背景下能源低碳化技术综述及对新型电力系统发展的启示[J]. 中国电机工程学报, 2021, 41(S1): 28-51.
	HUANG Y H, DING T, LI Y T, et al. Decarbonization technologies and inspirations for the development of novel power systems in the context of carbon neutrality[J]. Proceedings of the CSEE, 2021, 41(S1): 28-51.
2	钱建国, 孔飘红, 章晓锘. 双碳背景下新型电力系统储能设计与运行[J]. 储能科学与技术, 2022, 11(12): 4102-4103.
	QIAN J G, KONG P H, ZHANG X N. Energy storage design and operation of new power system under the background of double carbon[J]. Energy Storage Science and Technology, 2022, 11(12): 4102-4103.
3	张宏霞, 张衍杰, 马茜, 等. "双碳"目标下新能源产业发展趋势[J]. 储能科学与技术, 2022, 11(5): 1677-1678.
	ZHANG H X, ZHANG Y J, MA (Q /X), et al. Development trend of new energy industry under the goal of "double carbon"[J]. Energy Storage Science and Technology, 2022, 11(5): 1677-1678.
4	FAISAL M, HANNAN M A, KER P J, et al. Review of energy storage system technologies in microgrid applications: Issues and challenges[J]. IEEE Access, 2018, 6: 35143-35164.
5	杨水丽, 来小康, 丁涛, 等. 新型储能技术在弹性电网中的应用与展望[J]. 储能科学与技术, 2023, 12(2): 515-528.
	YANG S L, LAI X K, DING T, et al. Application and prospect of new energy storage technologies in resilient power systems[J]. Energy Storage Science and Technology, 2023, 12(2): 515-528.
6	申洪, 周勤勇, 刘耀, 等. 碳中和背景下全球能源互联网构建的关键技术及展望[J]. 发电技术, 2021, 42(1): 8-19.
	SHEN H, ZHOU Q Y, LIU Y, et al. Key technologies and prospects for the construction of global energy Internet under the background of carbon neutral[J]. Power Generation Technology, 2021, 42(1): 8-19.
7	许守平, 李相俊, 惠东. 大规模储能系统发展现状及示范应用综述[J]. 电网与清洁能源, 2013, 29(8): 94-100, 108.
	XU S P, LI X J, HUI D. A survey of the development and demonstration application of large-scale energy storage[J]. Power System and Clean Energy, 2013, 29(8): 94-100, 108.
8	蒋凯, 李浩秒, 李威, 等. 几类面向电网的储能电池介绍[J]. 电力系统自动化, 2013, 37(1): 47-53.
	JIANG K, LI H M, LI W, et al. On several battery technologies for power grids[J]. Automation of Electric Power Systems, 2013, 37(1): 47-53.
9	YANG Z G, ZHANG J L, KINTNER-MEYER M C W, et al. Electrochemical energy storage for green grid[J]. Chemical Reviews, 2011, 111(5): 3577-3613.
10	ROBERTS B P, SANDBERG C. The role of energy storage in development of smart grids[J]. Proceedings of the IEEE, 2011, 99(6): 1139-1144.
11	林靖, 王晟, 李浩秒, 等. 液态金属电池的温度特性[J]. 中国电机工程学报, 2021, 41(4): 1458-1468, 1551.
	LIN J, WANG S, LI H M, et al. Temperature characteristics of liquid metal batteries[J]. Proceedings of the CSEE, 2021, 41(4): 1458-1468, 1551.
12	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.
13	TIAN Y H, ZHANG S Q. The renaissance of liquid metal batteries[J]. Matter, 2020, 3(6): 1824-1826.
14	MENG J W, ZHANG Y, ZHOU X J, et al. Li₂CO₃-affiliative mechanism for air-accessible interface engineering of garnet electrolyte via facile liquid metal painting[J]. Nature Communications, 2020, 11: 3716.
15	MENG J W, LI C L. Planting CuGa₂ seeds assisted with liquid metal for selective wrapping deposition of lithium[J]. Energy Storage Materials, 2021, 37: 466-475.
16	ZHANG Y, MENG J W, CHEN K Y, et al. Garnet-based solid-state lithium fluoride conversion batteries benefiting from eutectic interlayer of superior wettability[J]. ACS Energy Letters, 2020, 5(4): 1167-1176.
17	LIU Y Y, MENG J W, LEI M, et al. Alloyable viscous fluid for interface welding of garnet electrolyte to enable highly reversible fluoride conversion solid state batteries[J]. Advanced Functional Materials, 2023, 33(4): 2208013.
18	WU S, ZHANG X, WANG R Z, et al. Progress and perspectives of liquid metal batteries[J]. Energy Storage Materials, 2023, 57: 205-227.
19	刘奇, 刘双宇, 王博, 等. 液态金属电池研究进展[J]. 电源技术, 2019, 43(12): 2053-2057.
	LIU Q, LIU S Y, WANG B, et al. Research progress in liquid metal batteries[J]. Chinese Journal of Power Sources, 2019, 43(12): 2053-2057.
20	KIM H, BOYSEN D A, NEWHOUSE J M, et al. Liquid metal batteries: Past, present, and future[J]. Chemical Reviews, 2013, 113(3): 2075-2099.
21	LI H M, YIN H Y, WANG K L, et al. Liquid metal electrodes for energy storage batteries[J]. Advanced Energy Materials, 2016, 6(14): 2075-2099.
22	黎朝晖, 朱方方, 李浩秒, 等. 液态金属电池研究进展[J]. 储能科学与技术, 2017, 6(5): 981-989.
	LI Z H, ZHU F F, LI H M, et al. Research progresses of liquid metal batteries[J]. Energy Storage Science and Technology, 2017, 6(5): 981-989.
23	孟潇, 张伟. 合金电极液态金属电池研究进展[J]. 电源技术, 2022, 46(5): 480-483.
	MENG X, ZHANG W. Research progress of liquid metal batteries with alloy electrodes[J]. Chinese Journal of Power Sources, 2022, 46(5): 480-483.
24	KANE M M, NEWHOUSE J M, SADOWAY D R. Electrochemical determination of the thermodynamic properties of lithium-antimony alloys[J]. Journal of the Electrochemical Society, 2014, 162(3): A421-A425.
25	NING X H, PHADKE S, CHUNG B, et al. Self-healing Li-Bi liquid metal battery for grid-scale energy storage[J]. Journal of Power Sources, 2015, 275: 370-376.
26	WANG K L, JIANG K, CHUNG B, et al. Lithium-antimony-lead liquid metal battery for grid-level energy storage[J]. Nature, 2014, 514(7522): 348-350.
27	NEWHOUSE J M. Modeling the operating voltage of liquid metal battery cells[D]. Massachusetts Institute of Technology, 2014.
28	MASSET P J, GUIDOTTI R A. Thermal activated ("thermal") battery technology[J]. Journal of Power Sources, 2008, 178(1): 456-466.
29	CAIRNS E, CROUTHAMEL C, FISCHER A K, et al. Galvanic cells with fused-salt electrolytes[R]. Argonne National Lab., Ⅲ., 1967.
30	SPATOCCO B L, OUCHI T, LAMBOTTE G, et al. Low-temperature molten salt electrolytes for membrane-free sodium metal batteries[J]. Journal of the Electrochemical Society, 2015, 162(14): A2729-A2736.
31	KIM H, BOYSEN D A, OUCHI T, et al. Calcium-bismuth electrodes for large-scale energy storage (liquid metal batteries)[J]. Journal of Power Sources, 2013, 241: 239-248.
32	OUCHI T, KIM H, NING X H, et al. Calcium-antimony alloys as electrodes for liquid metal batteries[J]. Journal of the Electrochemical Society, 2014, 161(12): A1898-A1904.
33	BRADWELL D J. Liquid metal batteries: ambipolar electrolysis and alkaline earth electroalloying cells[D]. Massachusetts Institute of Technology, 2011.
34	HOLUBOWITCH N E, MANEK S E, LANDON J, et al. Cathode candidates for zinc-based thermal-electrochemical energy storage[J]. International Journal of Energy Research, 2016, 40(3): 393-399.
35	HOLUBOWITCH N E, MANEK S E, LANDON J, et al. Molten zinc alloys for lower temperature, lower cost liquid metal batteries[J]. Advanced Materials Technologies, 2016, 1(3): 1600035.
36	HOLUBOWITCH N, MANEK S, LANDON J, et al. Zn-Sn electrochemical cells with molten salt eutectic electrolytes and their potential for energy storage applications[J]. ECS Transactions, 2014, 64(4): 439-452.
37	MATSUNAGA S, ISHIGURO T, TAMAKI S. Thermodynamic properties of liquid Na-Pb alloys[J]. Journal of Physics F: Metal Physics, 1983, 13(3): 587-595.
38	NEALE F E, CUSACK N E. Thermodynamic properties of liquid sodium-caesium alloys[J]. Journal of Physics F: Metal Physics, 1982, 12(12): 2839-2850.
39	WEAVER R D, SMITH S W, WILLMANN N L. The Sodium∣Tin liquid-metal cell[J]. Journal of the Electrochemical Society, 1962, 109(8): 653.
40	BRADWELL D J, KIM H, SIRK A H C, et al. Magnesium-antimony liquid metal battery for stationary energy storage[J]. Journal of the American Chemical Society, 2012, 134(4): 1895-1897.
41	LEUNG P, HECK S C, AMIETSZAJEW T, et al. Performance and polarization studies of the magnesium-antimony liquid metal battery with the use of in-situ reference electrode[J]. RSC Advances, 2015, 5(101): 83096-83105.
42	THACKERAY M M, WOLVERTON C, ISAACS E D. Electrical energy storage for transportation-Approaching the limits of, and going beyond, lithium-ion batteries[J]. Energy & Environmental Science, 2012, 5(7): 7854-7863.
43	UKSHE E A, BUKUN N G. The dissolution of metals in fused halides[J]. Russian Chemical Reviews, 1961, 30(2): 90-107.
44	DWORKIN A S, BRONSTEIN H R, BREDIG M A. Miscibility of metals with salts. vi. lithium-lithium halide systems¹[J]. The Journal of Physical Chemistry, 1962, 66(3): 572-573.
45	LI H M, WANG K L, ZHOU H, et al. Tellurium-tin based electrodes enabling liquid metal batteries for high specific energy storage applications[J]. Energy Storage Materials, 2018, 14: 267-271.
46	WEPPNER W, HUGGINS R A. Determination of the kinetic parameters of mixed-conducting electrodes and application to the system Li₃Sb[J]. Journal of the Electrochemical Society, 1977, 124(10): 1569-1578.
47	XIE H L, CHEN Z Y, CHU P, et al. An elaborate low-temperature electrolyte design towards high-performance liquid metal battery[J]. Journal of Power Sources, 2022, 536: 231527.
48	YAN S, ZHOU X B, LI H M, et al. Utilizing in situ alloying reaction to achieve the self-healing, high energy density and cost-effective Li\|\|Sb liquid metal battery[J]. Journal of Power Sources, 2021, 514: 230578.
49	LI H M, WANG K L, CHENG S J, et al. High performance liquid metal battery with environmentally friendly antimony-tin positive electrode[J]. ACS Applied Materials & Interfaces, 2016, 8(20): 12830-12835.
50	ZHAO W, LI P, LIU Z W, et al. High-performance antimony-bismuth-tin positive electrode for liquid metal battery[J]. Chemistry of Materials, 2018, 30(24): 8739-8746.
51	CUI K X, ZHAO W, LI S W, et al. Low-temperature and high-energy-density Li-based liquid metal batteries based on LiCl-KCl molten salt electrolyte[J]. ACS Sustainable Chemistry & Engineering, 2022, 10(5): 1871-1879.
52	XIE H L, CHU P, YANG M N, et al. A novel Sb-Zn electrode with ingenious discharge mechanism towards high-energy-density and kinetically accelerated liquid metal battery[J]. Energy Storage Materials, 2023, 54: 20-29.
53	DAI T, ZHAO Y, NING X H, et al. Capacity extended bismuth-antimony cathode for high-performance liquid metal battery[J]. Journal of Power Sources, 2018, 381: 38-45.
54	KIM J, SHIN D, JUNG Y, et al. LiCl-LiI molten salt electrolyte with bismuth-lead positive electrode for liquid metal battery[J]. Journal of Power Sources, 2018, 377: 87-92.
55	李浩秒, 周浩, 王康丽, 等. 液态金属电极的电化学储能应用[J]. 电化学, 2020, 26(5): 663-682.
	LI H M, ZHOU H, WANG K L, et al. Liquid metal electrodes for electrochemical energy storage technologies[J]. Journal of Electrochemistry, 2020, 26(5): 663-682.
56	ZHANG J, HUANG J, LIU R X, et al. Corrosion behaviour of AlN ceramics in LiF-LiCl-LiBr-Li molten salt at 500 ℃‍[J]. Corrosion Science, 2021, 190: 109672.
57	LI B R, WEN B, CHEN H Z, et al. Corrosion behaviour and related mechanism of lithium vapour on aluminium nitride ceramic[J]. Corrosion Science, 2021, 178: 109058.
58	MASSET P. Iodide-based electrolytes: A promising alternative for thermal batteries[J]. Journal of Power Sources, 2006, 160(1): 688-697.
59	TORTORELLI P F, CHOPRA O K. Corrosion and compatibility considerations of liquid metals for fusion reactor applications[J]. Journal of Nuclear Materials, 1981, 103: 621-632.
60	MENG X C, ZUO G Z, REN J, et al. Study of the corrosion behaviors of 304 austenite stainless steel specimens exposed to static liquid lithium at 600 K[J]. Journal of Nuclear Materials, 2016, 480: 25-31.
61	蒋凯, 黎朝晖, 王康丽, 等. 耐腐蚀密封绝缘装置及中高温储能电池: CN205960043U[P]. 2017-02-15.
	JIANG K, LI Z H, WANG K L, et al. Corrosion-resistant sealed insulation device and well high temperature energy storage battery: CN205960043U[P]. 2017-02-15..
62	GUO Z L, ZHANG Y, HE Y L, et al. Thermal power characteristics of a liquid metal battery[J]. Energy Reports, 2021, 7: 1221-1230.
63	GUO Z L, XU C, LI W, et al. Numerical study on the thermal management system of a liquid metal battery module[J]. Journal of Power Sources, 2018, 392: 181-192.
64	ZHANG Y, WANG S, GUO Z L, et al. A multi-input single-output thermal management system design for liquid metal batteries[J]. Applied Thermal Engineering, 2023, 219: 119575.

电极	电解质组成	比例(摩尔比)	熔点/℃	密度/(g/cm³)	电导率/(S/cm)	参考文献
Li	LiCl-KCl	41∶59	353			[24]
	LiCl-LiF	70∶30	501	1.8		[24-25]
	LiF-LiCl-LiI	20∶50∶30	430			[26]
	LiF-LiCl-LiBr	22∶31∶47	443	2.7	3.0	[26]
	LiBr-KBr	60∶40	320			[27-28]
	LiF-LiBr-KBr	3∶63∶34	312			[27-28]
Na	NaF-NaCl-NaI	15∶32∶53	530	2.54	1.7～2.0	[29]
Na	NaOH-NaI	80∶20	220			[30]
Ca	LiCl-NaCl-CaCl₂	38∶27∶35	450	1.85	2.6	[31-32]
Ca	LiCl-NaCl-CaCl₂-BaCl₂	29∶20∶35∶16	390	2.24	1.8	[31]
Zn	ZnCl₂	100	292			[33]
Zn	ZnCl₂-KCl	50∶50	230			[34-36]

[1]	闫苏, 钟芳芳, 刘俊伟, 丁美, 贾传坤. 高能量密度液流电池关键材料与先进表征[J]. 储能科学与技术, 2024, 13(1): 143-156.
[2]	欧阳意梅, 赵蒙蒙, 钟贵明, 彭章泉. 电化学储能界面的核磁共振谱学研究方法[J]. 储能科学与技术, 2024, 13(1): 157-166.
[3]	张力菠, 王格格. 电化学储能电池技术主题识别、演化及风险分析[J]. 储能科学与技术, 2023, 12(8): 2680-2692.
[4]	李凌萱, 王子轩, 赵辰孜, 张睿, 卢洋, 黄佳琦, 陈爱兵, 张强. 复合金属锂负极的定量模型新进展[J]. 储能科学与技术, 2023, 12(7): 2059-2078.
[5]	赵光金, 李博文, 胡玉霞, 董锐锋, 王放放. 退役动力电池梯次利用技术及工程应用概述[J]. 储能科学与技术, 2023, 12(7): 2319-2332.
[6]	黄渭彬, 张彪, 范金成, 杨伟, 邹汉波, 陈胜洲. ZIF-8复合PEO基固态电解质的制备与改性研究[J]. 储能科学与技术, 2023, 12(4): 1083-1092.
[7]	程志翔, 曹伟, 户波, 程云芳, 李鑫, 姜丽华, 金凯强, 王青松. 储能用大容量磷酸铁锂电池热失控行为及燃爆传播特性[J]. 储能科学与技术, 2023, 12(3): 923-933.
[8]	张宣梁, 何霆, 朱文龙, 王屾, 曾建华, 徐泉, 牛迎春. 基于多循环特征的储能电池SOH估计模型[J]. 储能科学与技术, 2023, 12(11): 3488-3498.
[9]	董乐贤, 郑群, 黄悦, 田志鹏, 刘建平, 王超, 梁波, 雷励斌. 管状固体氧化物燃料电池前沿技术研究进展[J]. 储能科学与技术, 2023, 12(1): 131-138.
[10]	刘阳, 滕卫军, 谷青发, 孙鑫, 谭宇良, 方知进, 李建林. 规模化多元电化学储能度电成本及其经济性分析[J]. 储能科学与技术, 2023, 12(1): 312-318.
[11]	沈馨, 张睿, 赵辰孜, 武鹏, 张羽彤, 张俊东, 范丽珍, 刘全兵, 陈爱兵, 张强. 金属锂电池中力-电化学机制研究进展[J]. 储能科学与技术, 2022, 11(9): 2781-2797.
[12]	李泓, 张强. 蓄势赋能谋发展，勇毅笃行谱新篇[J]. 储能科学与技术, 2022, 11(9): 2691-2701.
[13]	曹志成, 周开运, 朱家立, 刘高明, 严慜, 汤舜, 曹元成, 程时杰, 张炜鑫. 锂离子电池储能系统消防技术的中国专利分析[J]. 储能科学与技术, 2022, 11(8): 2664-2670.
[14]	林楠, KREWER Ulrike, ZAUSCH Jochen, STEINER Konrad, 林海波, 冯守华. 电化学能量储存和转换体系多物理场模型的建立及其应用[J]. 储能科学与技术, 2022, 11(4): 1149-1164.
[15]	赵志伟, 杨智, 彭章泉. 飞行时间二次离子质谱在锂基二次电池中的应用[J]. 储能科学与技术, 2022, 11(3): 781-794.